Micellar-Enhanced Ultrafiltration of Palladium and Platinum Anions

BY

Gwicana Sakumzi

A dissertation submitted in fulfilment of the requirements for the degree of

MASTER OF TECHNOLOGY: CHEMISTRY

in the Faculty of Science at the

NELSON MANDELA METROPOLITAN UNIVERSITY

January 2007

Supervisor: Dr N.M. Vorster

TABLE OF CONTENTS

Acknowledgements .................................................................................. i Summary .............................................................................................. ii Abbreviations ........................................................................................... iv List of Figures........................................................................................... v List of Tables............................................................................................ viii

CHAPTER ONE 1. Introduction .......................................................................................... 1 1.1. Background to waste treatment .................................................... 1 1.2. Definition of a hazardous waste.................................................... 2 1.3. Overview of platinum group metals............................................... 2 1.3.1. Occurrence and Origin........................................................... 3 1.3.2. Abundance and Distribution................................................... 3 1.3.3. Chemical properties............................................................... 5 1.3.4. Basic coordination chemistry of platinum and palladium ....... 5 1.3.5. Industrial applications of PGMs ............................................. 6 1.3.5.1. Catalysis ......................................................................... 6 1.3.5.2. Jewellery ........................................................................ 7 1.3.5.3. Electronics...................................................................... 7 1.4. Surfactants.................................................................................... 8 1.4.1. Overview................................................................................ 8 1.4.2. Classification of surfactants ................................................... 12 1.4.3. Industrial applications of surfactants...................................... 12 1.5. Membranes ................................................................................... 13 1.5.1. Overview................................................................................ 13 1.5.2. Typical membrane properties ................................................ 15 1.5.3. Classification of membranes.................................................. 15 1.5.4. Membrane modules ............................................................... 18 1.5.5. Pressure-driven membrane filtration processes .................... 19 1.5.6. Ultrafiltration system .............................................................. 20 1.5.6.1. Micellar-enhanced ultrafiltration system ......................... 21

1.6. Research objectives...................................................................... 23 CHAPTER TWO 2. Experimental and Key Performance Aspects...................................... 24 2.1. Materials ....................................................................................... 24 2.2. Synthetic procedures .................................................................... 25 2.2.1. Preparation of surfactant solutions ........................................ 25 2.2.2. Preparation of surfactant/metal ion solutions......................... 25 2.2.3. Membrane module preparation.............................................. 25 2.3. Apparatus...................................................................................... 27 2.3.1. Ultrafiltration system set-up ................................................... 27 2.3.2. Major components of ultrafiltration system ............................ 29 2.3.2.1. Membrane module ......................................................... 29 2.3.2.2. Peristaltic pump .............................................................. 30 2.3.2.3. Controlled temperature bath........................................... 30 2.3.2.4. Operation of MEUF......................................................... 30 2.4. Analytical techniques .................................................................... 31 2.4.1. Ultraviolet-visible spectrophotometer (UV-VIS) ..................... 31 2.4.1.1. Cetylpyridinium chloride calibration curve ...................... 31 2.4.2. Inductively Coupled Plasma Mass Spectrometry (ICP-MS)... 32 2.4.3. Conductometer ...................................................................... 33 2.5. Key Performance Aspects of the Ultrafiltration system ................. 33 2.5.1. Principle and Operation of MEUF system.............................. 33 2.5.2. Assessment and monitoring of the membrane condition....... 34 2.5.3. Regeneration of an ultrafiltration membrane ......................... 35 2.5.4. Fouling in membrane processes............................................ 36 2.5.4.1. Factors affecting fouling ................................................. 36 2.5.4.2. Common fouling problems.............................................. 36 2.5.5. Membrane cleaning ............................................................... 37 CHAPTER THREE 3. Preliminary investigation of metal ion and surfactant retention ............ 39 3.1. Definitions ..................................................................................... 39 3.2. Influence of various parameters.................................................... 40 3.2.1. Effect of pressure variation .................................................... 40 3.2.2. Effect of temperature variation............................................... 42

3.2.3. Effect of cetylpyridinium chloride concentration variation ...... 44 3.3. Micellar-enhanced ultrafiltration of Pt (lV) and Pd (ll) anions ........ 45 3.3.1. Micellar-enhanced ultrafiltration of Pt (lV) and Pd (ll) anions in acidic medium ................................................................... 45 3.3.2. Micellar-enhanced ultrafiltration of Pt (lV) and Pd (ll) anions in neutral medium.................................................................. 48 3.3.3. Micellar-enhanced ultrafiltration of a mixture of Pt (lV) and Pd (ll) anions in neutral medium............................................ 50 3.3.4. Effect of an electrolyte on metal ion and surfactant retention 52 3.4. Membrane interaction ................................................................... 53 3.5. Summary of preliminary investigations ......................................... 55 CHAPTER FOUR 4. Investigation of cetylpyridinium chloride retention................................ 56 4.1. Overview....................................................................................... 56 4.2. Investigation of the effects of an electrolyte .................................. 56 4.2.1. Effects of hydrochloric acid concentration variation............... 57 4.2.2. Effects of nitric acid concentration variation .......................... 60 4.2.3. Effects of sodium chloride concentration variation ................ 62 4.3. Summary of CPC retention investigations .................................... 64 CHAPTER FIVE 5. The concept of micellisation and conductivity investigations ............... 65 5.1. The concept of micellisation.......................................................... 65 5.2. Conductivity study......................................................................... 66 5.2.1. Experimental determination of the critical micelle concentration of cetylpyridinium chloride ............................... 66 5.2.2. Experimental procedure......................................................... 66 5.2.3. Determination of the degree of ionization .............................. 68 5.3. Influence of an electrolyte on the cmc value and degree of ionisation ............................................................................... 69 5.3.1. Determination of cmc in the presence of HCl ........................ 69 5.3.2. Determination of cmc in the presence of Pd (ll) anions and aqua regia .............................................................................. 71 5.3.3. Determination of cmc in the presence of Pt (lV) anions and aqua regia .............................................................................. 72

5.5. Summary of the conductivity investigations .................................. 74 CHAPTER SIX 6. Improved conditions for the retention of metal ion and surfactant........ 75 6.1. Micellar-enhanced ultrafiltration of individual metal ions............... 75 6.1.1. Ultrafiltration of platinum (lV) anions...................................... 75 6.1.2. Ultrafiltration of palladium (ll) anions...................................... 77 6.2. Micellar-enhanced ultrafiltration of Pt (lV)-Pd (ll) mixture.............. 79 6.3. Membrane response during Pt/Pd mixture ultrafiltration ............... 82 6.3.1. CPC retention ........................................................................ 82 6.3.2. Flux variation ......................................................................... 83 6.4. Summary of the investigation of improved conditions..84 CHAPTER SEVEN 7. Conclusive remarks.............................................................................. 85 7.1. Conclusion .................................................................................... 85 7.2. Recommendations ........................................................................ 86 References.............................................................................................. 87 APPENDIX A ........................................................................................... 89 APPENDIX B ........................................................................................... 97 APPENDIX C ........................................................................................... 99 APPENDIX D ........................................................................................... 101

ACKNOWLEDGEMENTS

I wish to express my sincere thanks to:

Dr Nicole Vorster for her wonderful support, guidance and motivation. Prof EP Jacobs and Prof P. Loyson for their support. Dr E. Hosten for his assistance. A special tribute to my friends, Lwandile Mcingana, Akhona, Sivuyile, Chanda and Mtheza for their assistance and support throughout this study. My fellow students and co-workers at NMMU, and the entire PETCRU personnel for their assistance. Dr C. Viviers and Mr A. Joubert and co-workers at HCSA for their understanding and support. CCETSA, NRF and PET for their financial support. My mom and the entire family for their encouragement and support to carry out this work during the trying times.

The Almighty for making everything possible.

ii

EXECUTIVE SUMMARY

The project was concerned with studying the capability of a micellar-enhanced ultrafiltration system (MEUF) to remove platinum group metal ions namely Pt (lV) and Pd (ll) chloro anions from aqueous industrial waste effluents. South Africa has the worlds largest reserves of platinum group metals (PGMs) and other valuable metals such as manganese, chrome ores, titanium minerals etc. which are required for new automotive and other technologies, including fuel cells, catalytic converters and lighter components. The consistent loss with the industrial waste stream and the toxicological effects of these precious metals led to the need to develop new and effective methods to recover them from industrial waste effluents.

With such a wide variety of fields where these PGMs are used and the failure of the traditional techniques namely sedimentation, fermentation etc. to effectively reduce or recover these highly toxic and precious metal ions prior to discharging industrial waste effluents, it is necessary to explore other techniques such as membrane technology that can be used to recover these valuable species from industrial waste streams.

The present study involved the use of a cationic surfactant, viz cetylpyridinium chloride, which was introduced into an aqueous solution containing palladium and platinum metal anions. The surfactant forms charged micelles above a certain critical concentration value. The metal anions adsorb onto the available oppositely charged sites on the micelle surfaces and are then able to be retained by a suitable membrane. Hollow fibre ultrafiltration membranes with the MWCO of +/- 10 kD and +/-30nm pore size were used as a filter component in this study. For this MEUF system to be effective, it was vital that the anionic metal ion species adsorbed sufficiently onto the available oppositely charged sites of the micelles and that the micelles were retained efficiently by the membrane.

iii Results obtained during the investigation made it possible to make certain predictions about the micellisation process. It was also found that, it was not only the metal ion: surfactant (M:S) ratio that was critical, but the presence of other electrolytes in the aqueous stream proved to have a huge impact on the capability of the MEUF system.

Findings of this research study showed that the MEUF system using cetylpyridinium chloride (CPC) can be used to recover or retain Pt (lV) and Pd (ll) anions from industrial waste effluents. It was also found that PtCl62-, due to its greater adsorption capabilities onto the micelle surface than PdCl42- or PdCl3(H2O)-, was preferentially retained in neutral medium. This may be exploited as a possible means of separating the two metal ions.

The developed system offers the following advantages over some traditional and current methods: simplified unit operation line flow process, smaller amounts of chemical usage and no solid toxic sludge to be disposed of.

Applications of this work could be of vital importance in catalytic converter recycling, especially in Port Elizabeth where extensive automobile parts manufacturing occurs.

KEYWORDS: Platinum, palladium, micellar-enhanced ultrafiltration, surfactant,

micellisation, cetylpyridinium chloride

iv

ABBREVIATIONS

MEUF mM CPC PGMs cmc NaCl HCl HNO3 ICP-MS UV-VIS

Micellar-Enhanced Ultrafiltration Millimolar Cetylpyridinium chloride Platinum group metals Critical micelle concentration Sodium chloride Hydrochloric acid Nitric acid Inductively Coupled Plasma Mass Spectrophotometry Ultraviolet visible

LIST OF FIGURES

Figure 1.1: Worldwide distribution of PGMs Figure 1.2: Micelle formation in dilute solution Figure 1.3: Schematic diagram of a micelle Figure 1.4: Schematic diagram showing the occurrence of cmc with changing solution parameters Figure 1.5: A typical diagram showing the occurrence of a cmc value at the Kraft point with changing solution parameters Figure 1.6: Cetylpyridinium chloride structure Figure 1.7: Hollow fibre module Figure 1.8: Tubular module Figure 1.9: Pressure-driven membrane separation processes Figure 1.10: A mechanistic scheme showing the adsorption of an

4 9 9 10

11

12 18 18 19 22

anionic metal species such as Pt (lV) onto a cationic micelle Figure 2.1: SEM image of a cross section of the polysulfone hollow fibre 26 membrane Figure 2.2: SEM image of a part of the outer surface of the polysulfone 26 hollow fibre membrane Figure 2.3: Photo of a laboratory scale MEUF system Figure 2.4: Schematic diagram of an ultrafiltration system Figure 2.5: CPC calibration curve Figure 2.6: A typical layout of an ultrafiltration system Figure 2.7: Pure water flux measurements taken after various experiments Figure 3.1: Effects of pressure variation at 30C and 10 mM CPC Figure 3.2: Effects of temperature variation 150 kPa and 10 mM CPC Figure 3.3: Variation of CPC concentration at 30C and 150 kPa Figure 3.4: Investigation of Pt and Pd anions retention at 150 kPa and 30C in acidic medium as a function of CPC concentration Figure 3.5: Investigation of Pt and Pd anions retention at 150 kPa and 30C in neutral medium as a function of CPC concentration 48 41 42 44 46 28 29 32 34 35

vi Figure 3.6: Species distribution curves of Pd (ll)/chloride system Figure 3.7: Investigation of Pt and Pd anions separation in acidic 49 51

medium at 150 kPa, 30C as a function of CPC concentration Figure 3.8: Effects of sodium chloride on Pt and Pd anions retention Acidic medium at 150 kPa and 30C using 40 mM CPC Figure 3.9: Effects of various species on flux variation at 150 kPa and 30C in neutral medium Figure 4.1: Variation of hydrochloric acid concentration at 30C, 150 kPa and 10 mM CPC Figure 4.2: Variation of nitric acid concentration at 30C,150 kPa and 10 mM CPC Figure 4.3: Study of variation of sodium chloride concentration at 30C, 150 kPa and 10 mM CPC Figure 4.4: Surface tension of a 10 mM CPC solution as a function of HNO3 concentration Figure 4.5: Study of variation of sodium chloride acid concentration at 30C, 150 kPa and 10 mM CPC Figure 5.1: Determination of the cmc of CPC and its degree of ionisation Figure 5.2: Plot of the conductivity vs CPC concentration in the presence of HCl Figure 5.3: Plot of the conductivity vs CPC concentration in the presence of Pd (ll) anions in aqua regia Figure 5.4: Plot of the conductivity vs CPC concentration in the presence of Pt (lV) anions in aqua regia Figure 6.1: MEUF of Pt (lV) anions at 40 mM CPC, 30C and 150 kPa in acidic medium Figure 6.2: MEUF of Pd (lV) anions at 40 mM CPC, 30C and 150 kPa 78 in acidic medium Figure 6.3: MEUF of a mixture of Pd (lV)/Pt (lV) anions at 40mM CPC, 30C and 150 kPa in acidic medium Figure 6.4: MEUF of a mixture of Pt (lV)/Pd (lV) anions at 40 mM CPC, 81 30C and 150 kPa in acidic medium 80 76 73 71 70 67 63 62 61 59 58 54 52

vii Figure 6.5: Effects of metal ion ratio on CPC retention Figure 6.6: Flux variation during Pt (lV)/Pd (lV) anions ultrafiltration 82 84

viii

LIST OF TABLES

Table 1.1: Examples of common surfactants Table 1.2: Description of different types of membranes Table 1.3: Summary of membrane separation processes Table 2.1: List of Chemicals used for synthesis and analysis Table 2.2: Major components of a laboratory scale MEUF system Table 2.3: Membrane module specifications Table 2.4: Peristaltic pump specifications Table 2.5: ICP-MS settings Table 2.6: Membrane foulants and control measures Table 6.1: Summary of varying metal ion concentration ratios

12 16 20 24 28 29 30 33 37 79

CHAPTER ONE

INTRODUCTION

In this chapter, a brief overview on waste treatment, the chemistry and industrial applications of platinum group metals, surfactants and membranes will be given. The scope of this research study will also be outlined.

1.1 Background to waste treatment

In recent years, waste treatment has become a necessary activity of various industries, most importantly, of chemical industries. The major purpose of wastewater treatment is to remove as much of the suspended solids and hazardous materials present in waste streams prior to their disposal back to the environment. The emphasis on wastewater treatment has not only been generated by the negative impact that wastewater constituents impose on the community due to their toxic and harmful effects, but also by the huge profits that can be enjoyed by chemical industries from the recovery of waste materials. For some chemical industries, the recovered components can be

reprocessed, thus leading to higher yields of their products.

Stringent regulations after the introduction of an Environmental Management System (EMS) standard, namely the ISO 14001 series, require all industries to comply with the regulatory systems and to continuously improve wastewater treatment activities.1, 2 Since the costs and constraints of treatment systems can be unbearable, the necessity to reduce the content of these highly toxic as well as non-biodegradable constituents prior to discharging the waste stream into sewage is of vital importance. 3

It has been noted that the use of traditional techniques, namely lime precipitation, ion exchange, activated carbon adsorption, electrolytic processes etc. are ineffective in reducing the levels of carcinogenic components to the required levels as stipulated in the Environmental Management System.
2, 4

It has also been noted that the use of

membrane separation processes in wastewater treatment is an attractive, as well as a more preferred technique, especially in the chemical industry, than the previously mentioned methods. 1.2 Definition of a hazardous waste

Hazardous waste is defined as an organic or inorganic element or compound that due to its chemical, physical and toxicological properties may be deemed harmful and/or brings chronic impacts to human health and the environment.1 It can be generated from a variety of agricultural, commercial, domestic and industrial activities and may be in the form of a liquid, sludge or a solid. Within this hazardous waste there are inorganic pollutants such as platinum group metals that are considered to be highly toxic, non-biodegradable and which have definite carcinogenic effects.
3

These features contribute not only to the degree

of hazard, but are also of great importance in the ultimate choice of a safe and environmentally reasonable method of disposal or treatment. 1.3 Overview of platinum group metals (PGMs) 5, 6

Platinum group metals form part of the transition metal series. The group is made up of the following metals, namely, palladium, platinum, iridium, osmium, rhodium and ruthenium. Theoretically, platinum group metal ores are assumed to contain 20% of each of palladium, platinum, osmium and ruthenium and 6% of iridium and rhodium.

3 1.3.1 Occurrence and origin

The platinum group metals in the lithosphere have been transferred from the earths interior. Tectonic movements of the earths crust followed by the eruption of magma have led to the presence of PGMs in regions closer to the surface. Chemical interaction with silicate layers such as sulphides, arsenides, antimonide etc. at high temperatures has played a major role in the origination of platinum group metals. However, the PGMs later separated from ultrabasic magmas, hence the ores are sulphide free. Platinum and palladium, and sometimes together with nickel or copper, have undergone some hydrothermal reactions with chlorides in the earths interior which have led to the formation of the primary deposits of the platinum-bearing rock. Activities in those primary deposits depend on the following factors, namely, concentration of platinum metals present, accessibility, size of deposits, their value and the economic potential of the accompanying materials.

The platinum group metals occur mainly in ore deposits in a large number of minerals. Workable deposits usually contain mainly sperrylite (PtAs2), cooperite (PtS), ferroplatinum (Fe-Pt), polyxene (Fe-Pt-other PGMs) etc. These minerals are often associated with specific carrier materials such as iron pyrites, nickel iron pyrites, or chrome iron pyrites. These minerals as well as the platinum group metals are rarely found in exact stoichiometric ratios.
7, 8, 9

The platinum group metals, as already

stated, often occur in a very complex ore body in which they are bonded mainly to the so-called soft ligands such as sulphides or polysulphides, arsenides and selenides. 1.3.2 Abundance and Distribution

The abundance of platinum group metals, which occupy an intermediate position, based on their atomic number and atomic mass would be expected to be 10-4 ppm based on the manner of formation of their atomic nuclei.
8

A global distribution diagram of the platinum group

4 metals is shown in Fig. 1.1. South Africa is a leading producer of platinum group metals because it has the worlds largest reserves of PGMs. The worldwide distribution of the PGMs shows that there are only two countries, namely, South Africa and Russia, that produce a significant amount of these PGMs. 8 The main ore bodies in South Africa are owned by two companies, namely, Anglo American and Impala Platinum. The mining, refining and processing of these PGMs in South Africa does not only serve as a source of income for the country, it also brings about economic stability. 2

60.0% 50.0% 40.0% 30.0% 20.0% 10.0% 0.0% South Africa USA Russia Canada Finland China Zimbabwe Colombia

Figure 1.1: Worldwide distribution of platinum group metals

6, 9

It is also said

that, in South Africa, PGMs together with other by-

products namely gold, silver, nickel, copper and cobalt occur in economic concentrations in three extensive layered reefs associated with the mafic rocks of the Rustenburg layered suite of the Bushveld Complex. They are the Merensky reef, the UG2 Chromitite layer and the Platreef. Small quantities of the PGMs are also produced from gold deposits of the Witwatersrand Basin and from the copper ores of the Phalaborwa Complex. South Africas mineral wealth and the increasing demands of the platinum group metal products throughout the world, makes the process of hydrometallurgy vital. Also, the chemistry related to the dissolution of the ore of the PGMs, their successive separation

5 and ultimate production of the pure individual PGMs are thus very important for the economy of this country. 1.3.3 Chemical properties

The chemical properties of the platinum group metals resemble those of the late 4d and 5d transition metals as listed below: Platinum group metals have multiple oxidation states viz. Pt (ll), Pt (lV), Pd (ll), Pd (lV) etc. They show high covalent character in bonding. They have slow ligand exchange due to kinetic stability of their complexes. In their metallic form, the metals are inert and show great stability.

These above-mentioned properties greatly contribute towards the problematic nature of the dissolution, isolation and processing of PGMs. Also, these same characteristics make these metals suitable for a variety of applications, namely, catalysis, synthesis, etc.
7, 8, 10, 11

1.3.4 Basic coordination chemistry of platinum and palladium

7, 8

Palladium is a member of the 4d transition metal series while platinum falls within the 5d series. Palladium and platinum have the same number of electrons in their valence shell, viz. ten electrons in excess of the preceding noble gas (s0d10 for Pd and s1d9 for Pt). These metals have similar electron configurations since they belong in the sub-group that constitutes nickel, palladium and platinum. The most significant characteristic properties of the two metals are the kinetic stability of their complexes and the high covalent character of their bonding. These metals are known to prefer the soft donor ligands with covalent properties as opposed to hard donor ligands such as ammonia and aliphatic amines, and thus they show a greater preference for pi acceptor ligands like chloride, sulphur, arsenic and phosphorous donors.

6 Furthermore, the divalent metal complexes of these two metals are almost, without exception, spin-paired square planar d8 systems, while their tetravalent compounds are spin-paired octahedral d6 systems. Based on the previously mentioned identical behaviours of these two metals, it can be stated that these metals have similar preferences with respect to ligand selectivity and symmetry of their coordination compounds; and have similar electronic as well as magnetic properties.
8, 12

1.3.5 Industrial applications of platinum group metals

1.3.5.1 Catalysis

Platinum group metals are renowned for contributing towards a pollution free environment. They are extensively used in automobile catalytic converters where they catalyse the detoxification of nitrates and reduction of hydrocarbons in automobile exhaust gas emissions to acceptable low levels. They are also used in various complex catalytic processes such as aromatization, cracking, cyclisation, desulphurisation, hydrocracking, hydroprocessing and reforming in the petroleum industry to manufacture a wide variety of products.

Nitric acid that is used in the production of nitrogenous fertilizers (78%), and explosives (12%), is produced by catalytic oxidation of ammonia over gauzes woven from very fine platinum (90%)-rhodium/palladium (510%) alloy wire.
9

Similar catalysts are employed in the Andrussen and Degussa processes for the manufacturing of hydrogen cyanide from methane and ammonia. These plants produce nitrous oxides that are reduced by a platinum-impregnated catalyst contained either in a ceramic honeycomb, alumina-pellet or nickel-chromium alloy ribbon support.

PGMs are also used in processes involved in the manufacture of liquidphase chemicals which include:

Highly specific hydrogenation catalysts. Complex catalysts using polymeric supports to catalyze a whole spectrum of organic reactions. Metal-cluster catalysts in which organo-metallic compounds form cluster structures that can model biological catalysts. Oil from coal processes.

1.3.5.2 Jewellery 8, 12

In jewellery making processes, platinum offers the following advantages:

It is harder (4.3 on mohs scale) than gold and does not nick or scratch easily. It does not tarnish like silver. It holds gemstones better because of its superior strength and hardness.

However, it has one disadvantage in the form of a high melting point and thus has to be alloyed with rhodium in order to be suitable for jewellery setting. 1.3.5.3 Electronics 5, 12

Platinum is employed in electrical contacts that are used under severe conditions such as heavy-duty relays, switches, thermostats, voltage regulators and slip-ring assemblies. It is also used in making thin-film circuits, resistance elements, multilayer capacitors and oxygen sensors. Thermocouples employed in the steel and glass smelting industry use a fine-wire platinum/rhodium alloy for the positive electrode and a pure platinum wire for the negative electrode to provide a long life span and the highest degree of accuracy.

8 Palladium is used in capacitors as contact materials applying to any electrical contacts operating at low currents and voltages under low contact forces due to the reasons listed below:

Freedom from oxide films and tarnish. High melting temperature which results in a high resistance to arc erosion and to the welding of contact surfaces such as telephone switching relays, electrical and electronic apparatus, resistors, gas turbine engines and atomic reactors, spinnerets to produce rayon fibre, heating pads, high voltage regulators, relays, thermostats, sliding contacts, magnetos, vibrators and signs.

1.4. Surfactants

1.4.1 Overview

Surfactants are defined as molecules that are usually surface active in aqueous solutions.
13

These molecules adsorb strongly at the water-air

interface and subsequently lower the surface energy of water (However, inorganic electrolytes that are desorbed at the water air interface behave differently as they tend to slightly increase the surface energy of water). Surfactant molecules are amphiphilic in nature, that is, they have a charged head group that is hydrophilic and a hydrophobic hydrocarbon tail. It is this unique feature that makes surfactants adsorb so effectively at a surface interface. In dilute solutions, surfactant molecules are in the form of monomers. The number of monomers adsorbed at the surface increases with increasing surfactant concentration until the surface becomes saturated. At this saturation point called the critical micelle concentration, the monomers in the bulk solution aggregate to form micelles in order to minimize the exposure of the hydrophobic tail to the hydrophilic environment while maintaining the maximum interaction of the charged head group with the water. The resulting micelles are usually spherical in shape and range from 50 to 100 monomers as

9 shown in Fig. 1.2 below. An increase in surfactant concentration tends to increase the number of micelles per unit volume.

+ +

+ +

+ + +

+ + +

+ + +

+ + + +

Figure 1.2: Micelle formation in dilute solution

For a particular spherical micelle, the head (hydrophilic) groups are not closely packed on the surface of the micelle and calculations indicate that the head groups occupy not more than a third of the micelle surface (see Fig. 1.3). 13

Figure 1.3: Schematic diagram of a micelle 13

10 Repulsion between the head groups tends to increase the surface area hence some of the counter ions remain associated with the micelles so it is not fully ionized.

Above the critical micelle concentration (cmc) some of the surfactant solution properties such as conductivity, surface tension and viscosity suddenly change. This abrupt change in solution properties can be used as a means of determining the cmc (see Fig. 1.4).

cmc

Solution parameter

Surface tension

Electrical conductivity

Concentration of surfactant

Figure 1.4: Schematic diagram showing the occurrence of the cmc with changing solution parameters

Micelles are soluble in water but only above a certain temperature called the Kraft temperature. This is the triple point on the phase diagram of an ionic surfactant (see Fig. 1.5 below). Below this temperature and above the cmc the micelles form gels. The solubility of a surfactant generally depends on how easily it dissociates in water and how well the head group is solvated. The solubility generally increases with increasing temperature.

11

cmc

Monomer solution Micellar solution T

Kraft point Gel c Figure 1.5: A typical phase diagram of an ionic surfactant showing the cmc value at the Kraft point

There are a number of possible micelles shapes, namely, spherical, rodshaped or disk-shaped that can result when micellisation takes place. The shape of a micelle is determined mostly by the ratio of the area requirement of the head group of the surfactant under the prevailing conditions to the volume of the hydrophobic tail group. If this ratio is large, as in the case of n-alkyl surfactants, spherical surfactants are formed, whereas small ratios, such as in the case of nonionic alkyl polyglycol ethers, lead to the formation of rod-shaped micelles. Rodshaped micelles can also be formed by the addition of an electrolyte into ionic surfactant solutions that leads to the screening of the head groups electrostatic repulsive forces which result in a reduction of the headgroup area. Spherical micelles can also transform at higher surfactant concentrations into rod-shaped or disk-shaped micelles and this change is indicated by a second critical micelle concentration where there is a rapid change of colligative properties of a surfactant.13

12 1.4.2 Classification of surfactants

Surfactants can be classified into the following groups, namely, anionic (negatively charged head groups), cationic (positively charged head groups) and nonionic (no surface charge). Examples of each type are listed in Table 1.1 below.

Table 1.1: Examples of common surfactants Type Examples Sodium dodecyl sulphate Anionic Sodium dodecyl benzene sulphonate (SDS) Cetyltrimethylammonium Cationic bromide (CTAB) Cetylpyridinium chloride Nonionic Polyethylene oxide Chemical Formula CH3 (CH2)11SO4-Na+ CH3 (CH2)11C6H4SO3-Na+ CH3 (CH2)15N(CH3) 3+BrC21H38NCl CH3 (CH2)7(O.CH2CH2)8OH

The structure of the cationic surfactant, namely, cetylpyridinium chloride that was used for this research study is shown in Fig 1.6 below.

H3C Cl-

Figure 1.6: Cetylpyridinium chloride structure

14

1.4.3 Industrial applications of surfactants

Surfactants are considered to be of significant importance in various industries, namely, catalysis, detergent, emulsification, lubrication, oil recovery industry and the pharmaceutical industry. Some applications are listed below:

13 They have been used as solubilizing agents and as probes for the hydrophobic binding sites in the investigation of molecular properties of membrane proteins and lipoproteins. Surfactants have been used in the investigation of the denaturation and thermal stability experiments of bacteriorhodopsin. They are also employed to promote dissociation of proteins from nucleic acids on extraction from biological material. Surfactants have been used as useful reagents in analytical chemistry techniques, spectroscopy. 1.5 Membranes namely, chromatography and luminescence

1.5.1 Overview

Industrial and scientific development during the last 200 years has brought about a variety of industrial-scale separation techniques such as distillation, precipitation, crystallization, extraction, adsorption and ion exchange. However, processes that employ semi-permeable

membranes as separation barriers have recently supplemented these traditional techniques. Although membranes and membrane processes were initially introduced as an analytical tool in chemical and biomedical laboratories, they later developed into industrial products and methods with greater technical and commercial impact.15,16 A membrane is defined as an interphase that influences the transport of chemical species in a particular manner. A membrane structure has lateral dimensions much greater than its thickness, through which mass transfer may occur under a variety of driving forces. 17

There are several kinds of membranes that are currently in use, namely:
16

14 Membranes that are made from synthetic polymers (also copolymers and blends). Inorganic membranes that use inorganic porous supports and inorganic colloids such as zirconium oxide (ZrO2) or alumina with appropriate binders. Melt-spun thermal inversion membranes like hollow fibre

membranes and track-etched membranes.

The great majority of analytically important ultrafiltration membranes belong to the first type, that is, synthetic polymers. These membranes are usually made of polycarbonate, cellulose (esters), polyamide, and polysulphone. The greater interest recently in membrane separation processes originates from the simplicity of the systems, affordability in terms of cost, as well as their application in various fields namely, chemical, food, pharmaceutical as well as wastewater treatment industries.18 There are unique characteristics that influence the

membrane performance namely: selectivity, speed (flow rate with which the feed solution passes through the membrane) and the stability that relies mainly on the components that were used for the manufacturing of the membrane. Membranes are formed by various methods from numerous materials both of which profoundly influence the morphology and structure of the resulting product. Some of the industrial applications of membranes are listed below. 16

Membranes (e.g. ultrafiltration (UF), nanofiltration (NF), microfiltration (MF) and reverse osmosis (RO)) are used to treat industrial waste effluents to recover valuable constituents.

They

are

used

to

concentrate,

purify

and/or

fractionate

macromolecular solutions in various industries e.g. (UF and MF). They are used to produce potable water from seawater. They are used to remove urea and some other toxins from the bloodstream in the medical field (RO).

15 1.5.2 Typical membrane properties

A membrane can be heterogeneous or homogeneous and/or asymmetric or symmetric in structure. It may be liquid or solid, and can carry neutral, negative or positive charges. A membrane can have varying functional groups with different binding or complexing capabilities. Membrane thicknesses range from 100 nm to more than 1 cm. The electrical resistance of a membrane may vary from thousands of mega ohms to a fraction of an ohm.

1.5.3 Classification of membranes 15, 16

Membranes can be classified into five groups, namely, asymmetric, electrically charged barriers, homogeneous, liquid films with selective carriers and microporous membranes as shown in Table 1.2.

Membrane transport can be achieved by diffusion of individual molecules or through convection induced by the following variables, namely, concentration, pressure, temperature, or electrical potential gradient.16, 18

16 Table 1.2: Description of different types of membranes Membrane type Microporous Structure description Solid matrix Pore diameter: (20 m 1 nm) Materials used: Ceramics, Metals, and Polymers Separation process Sieving mechanism determined by pore diameter and particle size. Preparation techniques Sintering of powders, stretching of films, irradiation and etching of films and phase inversion techniques. Homogeneous Dense film through which a mixture of chemical species is transported under the driving force of concentration, pressure, etc. Asymmetric Thin skin layer (0.1 1 m) on a highly thick porous substructure (100 200 m) Separation performance determined by the nature of the membrane material or pore size Phase inversion process that leads to an integral structure deposition of a thin polymer film on a microporous substructure Mass transport occurs strictly by diffusion. Prepared from polymers, metals, or metal alloys by film-forming techniques.

17 Table 1.2 contd: Description of different types of membranes Membrane type Ion exchange Structure description Highly swollen gels carrying fixed positive or negative charges. Separation process Preparation techniques

Different organic Matrix that polymer matrices and functional groups determine the ion exchange properties. consists of a hydrophobic polymer such as polystyrene, polyethylene, or polysulphone. Fixed ionic moiety can be one of the following: SO3, COO, AsO3, NH3, -NH2, -NH, -N

Liquid films

Comprise a thin oil film separating two phases consisting of aqueous solutions or gas mixtures.

Use carriers to selectively transport components such as metal ions at a relatively high rate across the membrane interphase.

The pores of a microporous membrane are filled with the selective liquid barrier material or the membrane is stabilised as a thin oil film by a surfactant.

18 1.5.4 Membrane modules

19

Membranes can be formed into different configurations e.g. flat sheet, capillaries or hollow fibre. The advantage of a hollow fibre configuration is increased surface area. A number of capillary or hollow fibres can be bundled together to form a module. Fig. 1.7 and Fig. 1.8 show two types of membrane modules.

Figure 1.7: Hollow fibre module

Figure 1.8: Tubular module

19 1.5.4 Pressure-driven membrane filtration processes

Membrane separation processes can differ significantly with respect to membrane type, driving forces, areas of application and industrial or economic relevance. Ultrafiltration, microfiltration and reverse osmosis are the most important pressure-driven separation processes. The performance of a membrane in a pressure-driven separation process is determined by its filtration rate (i.e. transmembrane flux at certain hydrostatic pressure) and its mass separation properties (i.e. retention capability).

A summarized schematic diagram of pressure-driven membrane separation processes and examples of species that can be retained using those processes is shown in Fig. 1.9 below.

Figure 1.9: Pressure driven membrane separation processes 19

Membrane filtration processes can be applied to the treatment of industrial waste containing inorganic constituents, such as metal ions, at low concentrations.

20 The different membrane filtration processes are classified according to the type of chemical species that is to be retained, the corresponding membrane pore size that is required to retain that species and the applicable driving forces as shown in Table 1.3 below which lists the membrane processes in order of the type of species to be retained.

Table 1.3: Summary of pressure-driven membrane separation processes 16 Process Membrane type Driving force Separation method Application Sterile filtration, clarification

Microfiltration Symmetric

Hydrostatic Sieving mechanism due to pore radius and adsorption

microporous pressure membrane, 0.1 to 10 m pore radius Ultrafiltration difference, 10 to 500 kPa

Asymmetric, Hydrostatic Sieving microporous pressure membrane, 1 to 10 nm pore radius difference, 0.1 to 1 MPa Hydrostatic Solution pressure difference, 2 to 10 MPa diffusion mechanism mechanism

Separation of macromolecular solutions

Reverse osmosis

Asymmetric skin-type membrane

Separation of salts and microsolutes from solutions

1.5.6 Ultrafiltration

Ultrafiltration

is

one

of

the

several

pressure-driven

membrane

technologies. It can be used to separate small colloids and large

21 molecules from water and other aqueous media. The system is similar to microfiltration and differs only in the size of the separated particles and the membranes used. The ultrafiltration process falls between reverse osmosis and microfiltration in terms of the size of the particles removed, with ultrafiltration removing particles in the 0.002 to 0.1 micron range, and typically rejecting organics over 1000 molecular weight while the ions and smaller organics are allowed to pass through. A feed solution containing a mixture of components of different sizes is brought to the surface of a semi- permeable membrane. Under the driving force of a hydrostatic pressure gradient, solvent or small solutes permeate the membrane as filtrate while the larger particles or molecules and unbound ions are retained by the membrane and concentrated in the retentate. The separation is based solely on a sieving effect and particles are separated solely according to their dimensions. This process is regarded as an alternative to conventional and other traditional clarification techniques like flocculation, sedimentation, etc.20

1.5.6.1 Micellar-enhanced ultrafiltration for metal ion retention

Supported liquid membranes, where a complexing agent is added to an organic solvent contained in a porous hydrophobic membrane support have been applied to metal ion separation, but the use of these methods on an industrial scale is limited by the inherent instability of such membranes. Other techniques such as reverse osmosis and

nanofiltration membrane systems that are able to retain metal ions can also be applied but have limitations that are mainly due to their high costs which result from high transmembrane pressures and product fluxes which tend to be generally low.3

Micellar-enhanced ultrafiltration has been shown to be an effective method for the removal of low levels of toxic heavy metal ions and organic compounds from industrial waste effluents.4

22 In micellar-enhanced ultrafiltration, a surfactant is added to an aqueous solution containing the solutes of interest (metal ions) at a concentration higher than its critical micelle concentration (cmc) in order to capture ionic solutes. Once in solution, the surfactant forms large amphiphilic aggregate micelles with charged surfaces, ranging from 50 to 100 surfactant molecules. This phenomenon of micelle formation is called micellisation. The metal ions of opposite charge adsorb onto the charged micelle surface. The micelles increase the hydrodynamic size of the metal ion solutes that brings about their retention by the ultrafiltration membranes. See Fig 1.10 below.

Retentate

_
+ + +

_
+ + + +

_
+ +

_ + + + _ _
Permeate + PtCl62-

Cationic surfactant monomer

Figure 1.10: A mechanistic scheme showing the adsorption of an anionic metal species such as Pt (lV) onto a cationic micelle

Among the advantages of this method are the low-energy requirements of the ultrafiltration process and its high removal efficiency owing to the effective trapping of the metal ion solutes by the micelles. MEUF has been used to separate organic pollutants, heavy metals, chromates, nitrates and sulphates using both cationic and anionic surfactants as well as polyelectrolytes as additives.4, 21

23

1.6 Research objectives

In this research project, the ability of a membrane ultrafiltration system that is commonly used for the separation as well as the recovery of dissolved molecules or colloids in aqueous medium on the basis of molecular size was investigated for the retention of platinum group metals, namely, palladium and platinum. Within this membrane ultrafiltration system, a suitable cationic surfactant, namely,

cetylpyridinium chloride (CPC), was introduced in order to form colloidal aggregates that would increase the hydrodynamic size of the metal ions thus improving their retention by the system. The resulting process is referred to as micellar-enhanced ultrafiltration (MEUF). Variables such as pressure, temperature, pH, surfactant: metal ratio (S:M) and the effect of using electrolytes like sodium chloride were investigated in order to establish the conditions that can achieve the highest retention of platinum and palladium anions as well as surfactant from industrial waste streams.

24

CHAPTER TWO

EXPERIMENTAL AND KEY PERFORMANCE ASPECTS

In this chapter, the reagents, apparatus or equipment as well as analytical and synthetic procedures that were used during this research study will be described. The key performance aspects of the membrane module will also be explained.

2.1

Materials

All materials that were used in the preparation of synthetic solutions with their sources and respective grades are listed in Table 2.1 and were used without purification. Table 2.1: List of chemicals used for synthesis and analysis CHEMICAL NAME Cetylpyridinium chloride (98%) Dichloromethane Sodium hydroxide Hydrochloric acid (32%) Nitric acid (55%) Sodium hexachloroplatinate (lV) Potassium hexachoropalladate (IV) Sodium hypochlorite Potassium chloride Sodium chloride AR: Analytical reagent CP: Chemically pure NaOCl KCl NaCl Saarchem Saarchem Saarchem AR AR AR K2PdCl6 Aldrich CP CH2Cl2 NaOH HCl HNO3 Na2PtCl6 Saarchem Aldrich Saarchem Saarchem Aldrich AR AR AR AR CP FORMULA C21H38ClN.H2O SOURCE Aldrich GRADE AR

25

2.2 Synthetic procedures

2.2.1 Preparation of surfactant solutions

A calculated amount of cetylpyridinium chloride salt was weighed and dissolved in deionized water to make a 100 mM surfactant stock solution. Aliquot amounts were taken from the prepared stock solution to prepare surfactant solutions of different concentrations for ultrafiltration experiments. 2.2.2 Preparation of surfactant/metal solutions

1.0 mM metal stock solutions were prepared by dissolving calculated amounts of either Na2PtCl6 or K2PdCl6 salt in 5.0 ml aqua regia solution (vol. ratio HCl:HNO3 = 3:1) or other acid mixture in a small beaker and transferring into a 500 ml volumetric flask. These prepared stock solutions were used to prepare surfactant/metal solutions by taking aliquots of the metal stock solutions and adding them to various amounts of cetylpyridinium chloride. Other experimental variables such as pH, electrolyte concentration and temperature etc. were adjusted as required by the reaction conditions prior to the ultrafiltration process. 2.2.3 Membrane module preparation

A bundle of double skinned polysulphone hollow fibre membranes (twelve per unit) of approximately 30 nm pore sizes, 10 kD MWCO manufactured at the Institute of Polymer Science at Stellenbosch University was prepared and properly fitted into a stainless steel membrane tube. A quickset epoxy resin was used to seal the membranes into the tube in order to ensure that there were no leaks of metal feed solution during an ultrafiltration experiment. SEM images of the cross-section and surface of one of the hollow fibres were obtained

26 using the electron microscope in the Physics Department of the NMMU. These images are found in Figs. 2.1 and 2.2 respectively.

Figure 2.1: SEM image of a cross-section of the polysulphone hollow fibre membrane

Figure 2.2: SEM image of a part of the outer surface of the polysulphone hollow fibre membrane

27

2.3 Apparatus

A laboratory scale membrane ultrafiltration system was used in all ultrafiltration experiments carried out in this research study.

2.3.1 Ultrafiltration system set-up

The design of a membrane filtration system is very important as it determines the rates of physical transport phenomena associated with the chemical process or reaction, which in turn determines the outcome of the chemical reaction.22, 23 To have an ideal and uniform micellisation process occurring during the ultrafiltration experiments, the feed reservoir should have a sufficient volume to contain a certain amount of matter for a certain period of time. It should also offer the possibility for sufficient contact between the reactants. The feed metal ion solution was contained in a 300 cm3 beaker that was housed in a controlled temperature water bath and mechanically agitated. A four-bladed stirrer was used for agitation at approximately 300 rpm. A peristaltic pump was used to pump the feed solution through the membrane module, with the feed, retentate and permeate samples taken at specified intervals. A photograph of the laboratory scale ultrafiltration unit is shown in Fig. 2.3 and a diagrammatic representation is depicted in Fig. 2.4. Table 2.2 lists the major components of the system.

28

H F

90

E B
Figure 2.3: Photo of a laboratory scale MEUF system

Table 2.2: Major components of lab scale MEUF system Component A B C D E F G H Name Feed vessel Peristaltic pump Pressure gauge Membrane module Permeate vessel Pressure release valve Overhead stirrer Thermostat bath

29

Membrane (hollow fibre) in S/S casing Pressure gauge Peristaltic pump

Stirrer Retentate Permeate Pressure control valve Feed solution

Thermostat bath

Figure 2.4: Schematic diagram of MEUF system

2.3.2 Major components of Ultrafiltration system

2.3.2.1 Membrane module (D)

This unit is a stainless steel pipe that was used to house the polysulphone membranes used during the ultrafiltration process. It is about 38 cm long and is held firmly at a slight angle to the horizontal to allow continuous and uniform flow of the feed solution through the membrane and also to prevent the membranes from folding inside it and subsequently being damaged. A list of membrane filter unit

specifications is shown in Table 2.3.

Table 2.3: Membrane module specifications Variable No of fibres Length Value (units) 12 38 cm 0.024 m2

Outside diameter 2.0 mm Membrane Area

30

2.3.2.2 Peristaltic pump (B)

The pump was used to pump the feed solution through the membranes from the inside to the outside of each hollow fibre during the ultrafiltration process. It was driven at a constant speed of 45 rpm in all the ultrafiltration experiments. The pump played an important role as it helped to maintain the consistent flow of the feed solution in all the experiments. Peristaltic pump specifications are shown in Table 2.4 below. Table 2.4: Peristaltic pump specifications Variable Model Speed Operating Pressure Range Value (units) Gilsons Minipulse 3 0 - 48 rpm 0 - 600 kPa

2.3.2.3 Controlled temperature bath (H)

A stainless steel controlled temperature water bath was used to control and maintain a constant temperature in all the ultrafiltration experiments.

2.3.2.4 Operation of MEUF

The feed solution was pumped axially across the membrane surface to ensure tangential flow that reduces the concentration polarization phenomenon near the membrane surface. Permeate and retentate streams were recycled into the feed reservoir to maintain steady state conditions. Initial feed, retentate and permeate samples were collected after the completion of each ultrafiltration run and analysed for metal ion and surfactant content by Inductively Coupled Plasma Mass

31 Spectrometry (ICP-MS) and Ultraviolet-visible spectrophotometry

respectively. Every UF run was performed in duplicate, and the results averaged.

2.4 Analytical techniques

The methods that were employed for the analyses of the surfactant and platinum group metals together with the parameters and the instrumental settings are described below. 2.4.1 Ultraviolet visible spectrophotometry (UV-VIS)

UV-visible analysis of feed and permeate samples were performed on a Beckman DU-650 spectrophotometer to determine the surfactant content. A 0.1 cm quartz cell was used.
24, 25

The surfactant,

cetylpyridinium chloride absorbs in the UV region. The wavelength of maximum absorption occurs at 260 nm and this was thus chosen as the best wavelength for spectral analysis. Feed samples (20 ml) were taken from the untreated solution containing platinum group metals, prior to an ultrafiltration run while the permeate samples were taken at the permeate outlet at the end of each ultrafiltration run. 2.4.1.1 CPC calibration curve

Fig. 2.5 below shows the CPC calibration curve that was used throughout this study for the conversion of CPC absorbance data to concentration in units of mM. Calculated amounts of CPC salt were weighed and dissolved in deionised water to make up standards and analysed for CPC content by UV-VIS spectrophotometry at 260 nm against water as blank. The data pertaining to this experiment can be found in Appendix A, Table A1.

32

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 0.05 0.1 0.15 0.2 0.25

y = 4.219x R2 = 0.9992

ab s

CPC concentration (mM)

Figure 2.5: CPC calibration curve

2.4.2 Inductively coupled plasma mass spectrometry (ICP-MS)

8, 9, 26

Due to its sensitivity and low detection limit

, a Perkin-Elmer Sciex

6100 ICP-MS with a Perkin-Elmer AS 90 autosampler was chosen as the best instrument to perform analysis of the PGMs investigated in this research. A spectrascan certified multi element standard Au, Ir, Os, Pd, Pt, Re, Rh and Ru at 100 g/ml was used to prepare the standards ranging from 5.0 to 1000 g/L in 1% (v/v) of hydrochloric acid. Also, an In 1000 g/ml standard solution was used to prepare a 100 g/L In solution in 1% (v/v) hydrochloric acid. This In standard solution was mixed online and the In was used as an internal standard to counter the matrix effect. The instrumental settings of the Perkin Elmer ICP-MS are listed in Table 2.5 below.

33 Table 2.5: ICP-MS settings Parameter Nebuliser Flow rate RF power Detection limit Value (units) 0.71 L/min 1400 W 10 20 g/L

All the metal ion/surfactant samples were diluted either 100 or 200 times in order to fall within the detectable range of the ICP-MS for metal analysis and a second set diluted 40 or 100 times for UV-VIS surfactant analysis. 2.4.3 Conductometer

In this study, a Metrohm 660 conductometer with conductivity cell (model no. 6.0908.110) coupled with a platinum thermocouple electrode was used for conductivity measurements of the surfactant solutions with various additives.

2.5 Key Performance Aspects of the Ultrafiltration system

2.5.1 Principle and Operation of MEUF system

An untreated solution containing the micelles and the solutes of interest (PGMs) is forced against a semi-permeable membrane. The feed solution flows through the hollow fibre ultrafiltration membrane with pore sizes small enough to block the passage of micelles. The rejection of micelles brings about the removal of the solutes of interest while the unbound ions and surfactant monomers are able to pass through the ultrafiltration membrane to the permeate outlet. The operation of the MEUF system was performed in batch mode of 20 minute runs. Fig. 2.6 shows a typical batch mode operation.

34

Figure 2.6: A typical layout of a batch Ultrafiltration system

32

2.5.2 Assessment and monitoring of the membrane condition

It is vital that the membrane condition is kept the same for all ultrafiltration experiments, thus the membrane performance is measured prior and after each experiment by taking pure water flux (PWF) measurements. The pure water flux measurements before and after various ultrafiltration runs and after back flushing at 100 kPa are plotted against time as shown in Fig. 2.7 below. The pure water flux after each run with either Pt, Pd or CPC alone was significantly reduced indicating fouling of the membrane surface. However, after back flushing the membrane for about 15 minutes, the original pure water flux was restored. This indicates that the fouling is reversible.

35

100 80 P erm eate Flux (L/M 2h) 60 40 20 0 0 20 40 60 Time (minutes) Original PWF After backflushing After Pd run After CPC run After Pt run 80 100 120

Figure 2.7: Pure water flux measurements at 100 kPa taken after various ultrafiltration experiments 2.5.3 Regeneration of an ultrafiltration membrane 18,
30

During the ultrafiltration process, a membrane can either be permanently or temporarily damaged depending on the nature of the species that is being purified or recovered. This damage of the membrane can be due to membrane pore clogging which occurs as a result of a cake or gel layer formation on the membrane surface. However, a temporary gel layer due to concentration polarization onto the membrane surface is sometimes desirable as it helps to improve the retention of the targeted species. Although a temporary gel layer on the membrane surface can be reversed by back-flushing the membrane, a permanent cake or gel layer is not desired as it reduces the membrane performance.

36

2.5.4 Fouling in membrane processes

Fouling is the result of irreversible deposition or adsorption of solutes onto the membrane surface or pores. It has been established that an irreversible fouling may lead to the following: Flux decline Change in membrane selectivity and / or retention

2.5.4.1 Factors affecting fouling

The following factors can lead to fouling of a membrane: Unfavourable hydrodynamics Unfavourable membrane-solute interaction Membrane surface topography Hydrophilicity of the membrane Pore morphology and size distribution Membrane surface modification

2.5.4.2 Common fouling problems

A number of foulants that have been found to have a major impact in membrane fouling in various ultrafiltration processes are listed in Table 2.6 below.

37 Table 2.6: Membrane foulants and control measures Process Foulants Control measures Improve hydrodynamics. Generic Shear back flush. Air scouring. Controlled flux operation. Hydrocarbon surfactants Ultrafiltration and Microfiltration Proteins Limit concentration Control ionic environment, pH, use porous membranes Flux control Prefiltration Biological solids, bacteria, Use hydrophilic and more porous membranes

2.5.5 Membrane cleaning 18

Membrane cleaning is an essential requirement in membrane process applications. The frequency of cleaning entirely depends on the rate of fouling and operating protocol used, hence the cleaning may either be necessary after each ultrafiltration process or after months of continuous use of the membranes. The condition and performance of an ultrafiltration membrane are maintained by closely monitoring the pure water flux measurements. This can be approached in several ways, with the main aim being to minimize the adsorption of substances onto the membrane surface, thereby reducing the risk of shortening the lifespan of an ultrafiltration membrane, the amount of a cleansing reagent required, as well as the frequency of cleaning. Studies have shown that there is no specific technique that can prevent certain substances, such

38 as proteins, lipids, and phenolic substances from adsorbing onto the membrane surface.

Pure water flux measurements were taken prior to ultrafiltration experiments and used as a reference and also after each experimental run to monitor the condition of the ultrafiltration membrane. Upon observing that the pure water flux measurements deviated significantly from what they were prior to ultrafiltration experiments, necessary steps that involved the following were taken, namely:

Linear flush that can be used, for any membrane module for loosely bound species and is a useful step before applying chemical cleaning processes.

Backflushing the entire system with pure water with, or without, applied pressure. Using 0.1 mM of sodium hydroxide followed by 1.4 mM of hypochlorite and flushing with 1 mM of hydrochloric acid.

The procedure used for cleaning was found to be effective as it was able to restore the pure water flux measurements to their original and normal values that were used as reference measurements throughout the research studies.

39

CHAPTER THREE

PRELIMINARY INVESTIGATION OF SURFACTANT AND METAL ION RETENTION

This chapter involves the preliminary investigation of the factors which influence the retention of cetylpyridinium chloride by a specific ultrafiltration membrane. The capability of the micellar-enhanced ultrafiltration (MEUF) system to retain palladium (ll) and platinum (lV) anionic species with the aid of a cationic surfactant, namely, cetylpyridinium chloride, from synthetic aqueous solutions was also investigated as well as the possibility of separating these two metal ions from a synthetic mixture typical of the industrial waste effluent. The results are presented here in the form of graphs, with the data tables pertaining to each graph contained in Appendix A. 3.1 Definitions 18

Some of the key concepts or terms that will be used for discussion in this research study are defined below:

A membrane is a thin barrier or film between two phases that allows preferential transport of some species over others. Concentration polarization is the build-up of concentration of the species to be rejected near the membrane surface (Cm) leading to a higher concentration of the species near the membrane surface, (Cm) compared to the species concentration in the bulk of the solution, (Cb). This can lead to the formation of a temporary cake layer or in the worst case the formation of a permanent cake layer on the membrane surface.

40 Flux is the throughput of solution per unit area and is defined as follows: Jv = permeability x driving force, and is expressed as Litres/m2h (LMH) Retention (rejection) = (1 Cp/Cf) x 100% Cp: permeate concentration Cf : feed concentration Molecular weight cut off (MWCO) is the molecular mass of solute with 90% retention by the membrane.

3.2 Influence of various parameters

In this section, an investigation of the factors influencing the retention of the surfactant was done. Among the factors that were investigated were: pressure variation, temperature variation and the effect of increasing surfactant concentration.

3.2.1 Effect of pressure variation

This experiment was done in order to determine the pressure at which the best compromise between retention of the surfactant and permeate flux could be obtained. A set of cetylpyridinium chloride solutions of constant concentration (10 mM) was prepared by dissolving a calculated amount of CPC salt in water in a 250 ml volumetric flask and then transferring it into a suitable feed container for the ultrafiltration experiments. Ultrafiltration runs were done at various pressures ranging from 50 to 250 kPa. The temperature was kept constant at 30C in order to prevent any precipitation of the surfactant. Each ultrafiltration experiment was run for 20 minutes and at the end of each experiment, 20 ml permeate (P) and feed (F) samples were collected for CPC analysis by UV-VIS spectrophotometry. The results for this investigation are shown in Fig. 3.1 below with the data in Table A2 in Appendix A.

41

100.0 90.0 80.0

160.0 140.0

CPC retention (%)

70.0 60.0 50.0 40.0 30.0 40.0 20.0 10.0 0.0 0 50 100 150 200 250 20.0 0.0 300 100.0 80.0 60.0

Pressure (kPa) CPC retention Permeate flux

Figure 3.1: Effect of pressure variation at 10 mM CPC and 30C

From Fig. 3.1 it can be seen that cetylpyridinium chloride retention decreased slightly initially and then more dramatically beyond 150 kPa while the permeate flux increased continuously with increasing pressure up to 200 kPa after which it decreased. The decreasing retention with increasing pressure is a consequence of greater mass transport at higher pressures allowing more surfactant to pass through the membrane. This is also reflected by the increasing flux measurements with increasing pressure, up to 200 kPa. The sharp decline in flux at pressures greater than 200 kPa is due to concentration polarization near the membrane surface. A pressure of 150 kPa was chosen for all further experiments as this was seen to be the best compromise between permeate flux and retention.

Permeate Flux (L/m2h)

120.0

42 3.2.2 Effect of temperature variation

This investigation was done in order to establish a suitable temperature that would enable complete micellisation of CPC which would in turn lead to optimum retention of the surfactant. A set of cetylpyridinium chloride solutions of constant concentration (10 mM) was prepared by dissolving a suitable amount of CPC salt in deionised water in a 250 ml volumetric flask and then transferred into a suitable container that was used for ultrafiltration experiments. Ultrafiltration runs were done at various temperatures ranging from 10 to 50C. The pressure was kept constant at 150 kPa. Each ultrafiltration experiment was run for 20 minutes and at the end of each experiment, 20 ml permeate and retentate samples were collected for CPC analysis by UV-VIS spectrophotometry. Results for this investigation are shown in Fig. 3.2 below with the data in Table A3 in Appendix A.
90.0 80.0 70.0 CPC retention (%) 60.0 50.0 100.0 40.0 80.0 30.0 60.0 20.0 10.0 0.0 0.0 10.0 20.0 30.0 40.0 50.0 40.0 20.0 0.0 60.0 200.0 180.0 160.0 140.0 120.0 Permeate Flux (L/m2h)

Temperature (degrees)
CPC retention Permeate flux

Figure 3.2: Effect of temperature variation at 10 mM CPC and 150 kPa

43 Looking at Fig 3.2 above, it can be seen that at temperatures below 20C, cetylpyridinium chloride retention is very low, despite choosing a concentration value (10 mM) that is well above the critical micelle concentration that is required for this surfactant to form micelles. The low retention in this temperature region (0C to 20C) can be attributed to the fact that ionic surfactants only form micelles when the hydrocarbon chains are sufficiently fluid at temperature above the chain melting temperature. This temperature region is thus below the Kraft temperature, the point below which a surfactant becomes insoluble.

A significant increase in retention occurred at temperatures above 20C, with maximum retention, greater than 80%, achieved at around 30C. The higher retention observed at this point can be attributed to complete micellisation assumed to have occurred. However, beyond 30C a significant decrease in CPC retention was observed and this might be due to greater mass transport as a result of higher temperatures that permits the passage of the monomers and some micelles through the membrane pores.

However, while the CPC retention showed three different behaviours with increasing temperature, the flux measurements showed a continuous decrease with increasing temperature with a gradual levelling-off at higher temperatures. It can be assumed that the initial flux decline was due to increased numbers of micelles in solution and concentration polarization at the membrane surface which correlates with the increasing retention of surfactant. The latter levelling-off effect could be a result of partial membrane pore clogging due to the presence of micelles in the pores.

44 3.2.3 Effect of cetylpyridinium chloride concentration variation

A study to determine the surfactant concentration at which sufficient micellisation would occur was done. A set of cetylpyridinium chloride solutions of varying concentrations ranging from 0 to 45 mM was prepared by weighing suitable amounts of CPC salt. The respective salts were dissolved in deionised water in 250 ml volumetric flasks and then transferred into a suitable container that was used for ultrafiltration experiments. Ultrafiltration runs were done at a constant temperature (30C) and at a pressure of 150 kPa. A temperature of 30C was chosen as this was the temperature at which maximum retention of CPC occurred. Each ultrafiltration experiment was run for 20 minutes and at the end of each experiment, 20 ml permeate and retentate samples were collected for CPC analysis by UV-VIS spectrophotometry. The results for this investigation are shown in Fig. 3.3 below with the data in Table A4 in Appendix A.

70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0 0.0 10.0 20.0 30.0 40.0

120.0 100.0 80.0 60.0 40.0 20.0 0.0 50.0

CPC concentration (mM) CPC retention) Permeate flux

Figure 3.3: Effect of CPC concentration variation at 30 C and 150 kPa

Permeate Flux (L/m2h)

CPC retention (%)

100.0 90.0 80.0

160.0 140.0

45 From Fig. 3.3 above, it is quite clear that an increase in cetylpyridinium chloride concentration led to a continuous gradual increase in cetylpyridinium chloride retention. This consistent increase started at above 75% cetylpyridinium chloride retention in the lower concentration range of cetylpyridinium chloride (0 to 10 mM) with the maximum retention observed just above 95% at 45 mM cetylpyridinium chloride. The high cetylpyridinium chloride retention at greater CPC concentration can be ascribed to two factors, namely, concentration polarization and sufficient micellisation. As has been stated earlier, concentration polarization on the membrane surface is sometimes beneficial as it helps to enhance the retention of species of particular interest. It can also be said that the higher retention of cetylpyridinium chloride confirms that the very small number of monomers present in solution is due to fairly complete micellisation that is achieved with increasing concentration of cetylpyridinium chloride. While it was possible to achieve the desired high retention of cetylpyridinium chloride of more than 95% at 45 mM of cetylpyridinium measurements chloride, it was also observed that, the flux

decreased

sharply

with

increasing

surfactant

concentration and levelled at high CPC concentration. This product flux decline can be attributed initially to the increased number of micelles in solution as a result of an increased CPC concentration and finally to the concentration polarization phenomenon close to the membrane surface. 3.3 Micellar-enhanced ultrafiltration of Pt (lV) and Pd (ll) anions

Several experiments were performed in order to establish the effect of parameters such as the surfactant: metal ion ratio (S : M), the pH of the solution and the presence of an electrolyte on the retention of both the metal ions and the surfactant. 3.3.1 MEUF of Pt (lV) and Pd (ll) anions in acidic medium

This experiment was done in order to study the potential of the system to remove the metal anions of interest, viz, PtCl62- and PdCl42- from a

46 synthetic aqueous solution. The synthetic solutions were prepared by dissolving a suitable pre-weighed PGM chloride salt in aqua regia (vol ratio of HNO3 : HCl = 1: 3) solution and introducing various amounts of CPC solution as required per ultrafiltration run. For these experiments, the metal ion concentration was kept constant at 0.1 mM while the CPC concentration was varied from 0 to 40 mM. The temperature and pressure were kept constant at 30C and 150 kPa respectively. Each ultrafiltration experiment was done in duplicate and the samples were analysed as stated in section 2.4. The analysis data was averaged and used to construct the curves as shown in Fig. 3.4 below. The data can be obtained in Tables A5 and A6 in Appendix A.
120

100 M e tal i o n re ten tio n (% )

80

60

40

20

0 0 5 10 15 20 25 30 35 40 45

CPC concentration (mM) Pt retention Pd retention CPC retention in Pt (lV) CPC retention in Pd (lV)

Figure 3.4: Investigation of Pt and Pd anions retention at 150 kPa and 30C in acidic medium as a function of CPC concentration

Looking at the curves in Fig. 3.4 above, it is evident that, the MEUF system is able to retain the platinum group metal ions namely Pt (lV) and Pd (ll) from a synthetic solution similar to that of an industrial waste effluent. The retention of the two metal ions was very similar with a slight decrease in retention with increasing CPC concentration being observed

47 in both cases. The retention values for Pt (lV) decreased from 98.9% to 94.4% and for Pd (ll) from 98.8% to 95.5% as CPC values increased from 1 to 40 mM. However, although the MEUF system was able to achieve such high retentions for both metal ions, the retention of the surfactant (CPC) in the presence of each metal ion decreased significantly with the highest retention obtained at only 60% and the lowest retention well below 20%. This dramatic decline in cetylpyridinium chloride retention may be due to the presence of HCl and HNO3 in the solution. These acids are electrolytes and as stated in section 1.4.1 on p 11 electrolytes may affect the micellisation process and might cause the micelles to change their shape from a spherical shape to a rod-like structure with larger surface area but smaller diameter.13 These rods might be small enough to be able to pass through the membrane pores. The decline in CPC retention was greater in the Pt (lV) solution than in the Pd (ll) solution.

A possible explanation for the fact that the metal ion retention was close to 100% even though the surfactant retention was very low could be that the larger metal anions are partly responsible for the change in micelle shape due to their need for a larger surface area. Since the metal ion concentration is very low compared to the surfactant concentration, and their tendency to adsorb onto the metal surface is greater than that of supporting electrolyte, practically all metal ions are adsorbed from the solution. The hydrodynamic size of a micelle containing PdCl42- or PtCl62anions is larger than that of a micelle containing only chloride or nitrate anions, thus the metal-containing micelles are retained by the membrane while the remainder of the possibly rod-shaped micelles and unaggregated monomers pass through the pores. Another possible

explanation for the fact that the metal ions are retained so well could be the interaction of the metal anions with the charged head groups of surfactant molecules adsorbed at the membrane surface.3,4,21

The significant decline in cetylpyridinium chloride retention in the presence of the metal ions, led to a further investigation of the influence

48 of the different electrolytes on the retention of CPC. This will be dealt with in Chapter 4. 3.3.2 MEUF of Pt (lV) and Pd (ll) anions in neutral medium

Ultrafiltration of the PGMs in neutral medium was done in order to study the effect of pH on metal ion retention. The ultrafiltration solutions were prepared in the same manner as in 3.3.1 above except that the pH of the solutions was adjusted to a value of 7 +/- 0.02 using a 10% sodium hydroxide solution prior to starting each ultrafiltration experiment. The ultrafiltration runs were performed in duplicate and the data obtained from sample analysis were averaged and used to construct the curves as shown in Fig. 3.5 below. The data can be found in Tables A7 to A9 in Appendix A.

100.0 98.0 96.0 94.0 92.0 90.0 88.0 0 20 40 60 80 100 120

m e ta l i o n r e te n ti o n (% )

CPC concentration (mM) Pt retention Pd retention

Figure 3.5: Investigation of Pt and Pd anions retention at 150 kPa and 30C in neutral medium as a function of CPC concentration

49 It can be seen in Fig. 3.5 that in neutral medium there is a difference in the retention behaviour between Pd (ll) and Pt (lV), with Pt (lV) being retained to a greater extent than Pd (ll). This difference becomes more significant at higher CPC concentrations. However, both metal ions experience a decrease in retention with increasing CPC concentration. This could be related once again to the electrolyte effect, which has a bigger effect on retention values, in this case due the added Na+ ions.

Since it is well known that Pd (lV) immediately reduces to Pd (ll) in solution due to the instability of Pd (lV) solutions, species distribution curves of the Pd (ll) / Cl system as shown in Fig 3.6 below will be used to predict and explain the observations that occurred during the ultrafiltration of a mixture of Pt (lV) and Pd (ll) anions in aqueous solutions.

100 90 80 70 60 50 40 30 20 10 0 0

PdCl42PdCl3PdCl2 PdCl+

Pd2+

% of Pd(II)

4 p Cl

Figure 3.6: Species distribution curves of Pd/Chloride system (generated by IUPAC Stability Constant Database speciation software and Academic Software 2000)

IUPAC

50 From the species distribution curve, it can be seen that at pCl = 1 (chloride range in which solutions are prepared) Pd (ll) is present as PdCl42- and PdCl3(H2O)-. In neutral medium, OH activity is greater than in acidic medium, thus the possibility of forming hydrated mixed chloro/hydroxo species is greater. Also, ligand exchange of Pd (II) is 105 times faster than that of Pt (IV) since exchange can take place via an associative mechanism with a 5-coordinate intermediate for squareplanar Pd (II), which is 4-coordinated, whereas Pt (IV) tends to be octahedral (6-coordinated). Thus it is more likely that hydrated species are formed for Pd (II) rather than Pt (IV). Hydrated species are more hydrophilic and interact with water by hydrogen bonding and thus have a smaller tendency to associate with a micelle. This could account for the lower retention of Pd (ll) in neutral medium. 8,24,26

3.3.3 MEUF of a mixture of Pt (lV) and Pd (ll) anions in neutral medium

The experimental solutions were prepared by mixing equal quantities (0.1 mM each) of the two metal ions and varying the CPC concentration in the range of 0 to 100 mM. The pH of the ultrafiltration solutions was adjusted to a pH value of 7 0.2. Other experimental variables, namely, the pressure and temperature were kept at 150 kPa and 30C respectively. Samples were drawn at the end of each ultrafiltration run and prepared for the analysis of both metal ions (Pt and Pd) and the surfactant (CPC) as described in section 2.4. The results are presented in Fig. 3.7 below. The data can be found in Table A10 in Appendix A.

51
120.0 100.0 m etal ion retention (% ) 80.0 60.0 40.0 20.0 0.0 0 20 40 60 80 100 120

[CPC] mM Pd retention Pt retention

Figure 3.7: Investigation of Pt and Pd anions separation in neutral medium at 150 kPa, 30C as a function of CPC concentration

From a closer look at Fig. 3.7 above, it is evident that the system can be used to partially separate the two metal ions in a mixture at high CPC concentrations. High retention for Pt (lV) that was close to 100% throughout the studied CPC concentration range was obtained, while Pd (ll) was retained similarly at CPC concentration up to 20 mM with a significant decrease in its retention after 20 mM CPC concentration to reach a minimum value of around 80% at CPC concentration of 100 mM. Also, it can be noted that there was a maximum of about 20% difference in terms of the retention of the two metal ions, and this difference indicates a competition for adsorption on the available oppositely charged sites on the micelle surface with PtCl62- anions being preferentially adsorbed onto the micelles. This would be due to the reasons discussed in section 3.3.2.

52 3.3.4 Effect of an electrolyte on metal ion and surfactant retention

The experimental solutions were prepared as in section 3.3.1 above except that the CPC concentration was kept constant at 40 mM and varying amounts ranging from 0 to 100 mM of an electrolyte namely, sodium chloride were introduced into the metal ion (0.1 mM) and surfactant solutions prior to diluting them to the mark. The pH of the solutions was not adjusted and ranged between 4.6 and 5.3. Duplicate ultrafiltration runs were carried out as usual. Samples were taken and prepared for metal ion and CPC analysis. Sample analysis data was compiled accordingly and the averaged values were used to construct the curves shown in Fig. 3.8 below. The corresponding data tables are Table A11 (1) and Table A11 (4) in Appendix A.

120

100 m etal ion / CP C retention (% )

80

60

40

20

0 0.00

20.00

40.00

60.00 [NaCl] (mM)

80.00

100.00

120.00

Pd retention

Pt retention

CPC with Pd

CPC with Pt

Figure 3.8: Effects of sodium chloride on retention of Pt and Pd anions in acidic medium at 150 kPa and 30C using 40 mM CPC

It is well known that the industrial waste streams often contain some electrolytes that are used during chemical processing. Also, it is well known that the presence of electrolytes can influence the properties of a

53 surfactant13 and may affect the removal of the metal ions. It has been reported in literature,3,4,21 that the introduction of an electrolyte reduces the critical micelle concentration at which micelles form thereby increasing the number of micelles in solution and thus the micelle retention. Increased micelle retention was not observed here as can be seen in the curves in Fig. 3.8 above. The retention of the two metal ions remained fairly constant at above 90% throughout the sodium chloride concentration range. However, the retention of the surfactant was greatly reduced in the presence of sodium chloride especially during the ultrafiltration of platinum as it significantly decreased from just above 40% to just below 10%. This dramatic decrease in cetylpyridinium chloride retention cannot be attributed to the disruption of micellisation since the metal ion retention was still high in the presence of an electrolyte but might be due to a change of shape of the micelles from spherical to rod-like as it has been noted in section 3.3.1. Although during the ultrafiltration of palladium, the cetylpyridinium chloride retention was still higher at lower sodium chloride concentration range (0 to 30 mM) than in the ultrafiltration of platinum, it showed a consistent decrease after 40 mM sodium chloride concentration from just above 80% to close to 40%. It is clear that the Pt (lV) anion has a much greater effect on the retention of the CPC micelles than the Pd (ll) anions. This is possibly due to the double charge of the PtCl62- compared with PdCl3(H2O)-; the PtCl62- having a greater screening effect than PdCl3(H2O)- and thus might more readily promote a change of shape of the micelle.

3.4 Membrane interaction

Membrane interaction with a variety of species was also studied by carefully monitoring the variation of the permeate flux measurements during all the ultrafiltration runs. Flux data was compiled from duplicate measurements and the averaged values were used to construct the curves shown in Fig. 3.9 below. The data is found in Table A12.

54

140 120 Permeate Flux (L/M2hr) 100 80 60 40 20 0 0.0 20.0 40.0 60.0 [CPC] mM CPC alone CPC + 0.1 mM Pt CPC + 0.1 mM Pd CPC + 0.1 mM Pd/Pt mixture 80.0 100.0 120.0

Figure 3.9: Effect of various species on flux at 150 kPa and 30C

Flux decline followed the usual trend with the decrease in permeate flux observed with increasing surfactant concentration (from 0 to 100 mM). The initial steep flux decline can be attributed to an increased number of micelles in solution with increasing CPC concentration and the subsequent flatter portion of the curves is due to concentration polarization near the membrane surface. Based on these findings, it can be seen that working in a lower CPC concentration range up to 20 mM is more advantageous in order to achieve higher fluxes. Also, after each experimental run the membranes can be backwashed and/or cleaned with an alkali mixture in order to restore the membrane condition.

55 3.5 Summary of the preliminary investigations

CPC retention was linearly dependent on pressure up to 150 kPa after which the retention became less dependent on pressure increases.

It was found that it is important to maintain a temperature of 30oC in order to enhance the micellisation process. CPC retention increased with increasing initial surfactant

concentration and it was found that retention close to 100 % can be achieved above 40 mM surfactant concentration. The system was able to achieve a high retention of both Pd (ll) and Pt (lV) metal anions in acid medium. Pt (lV) retention in neutral medium was slightly greater than that of Pd (ll) and this was attributed to its greater adsorption onto the micelle surface than Pd (ll) due to Pd (ll) species being partially hydrated. Introduction of an electrolyte, namely, sodium chloride failed to improve the retention of both the metal ion and the surfactant, but in fact dramatically worsened the retention of CPC. The membrane responded differently in various mediums. This was shown by the flux variations of the various species. Although the system showed a great potential to retain both Pd (ll) and Pt (lV) anions from an aqueous solution, it failed to achieve optimum retention of the surfactant. This led to the investigation of conditions which affect the retention of CPC and the establishment of improved experimental conditions that would achieve higher retention of both the metal ion and surfactant. This investigation is described in the following chapter.

56

CHAPTER FOUR

INVESTIGATION OF CETYLPYRIDINIUM CHLORIDE RETENTION

4.1 Overview

This chapter focuses on an investigation of the effects of different electrolytes on cetylpyridinium chloride retention. This investigation was necessitated by the realization that cetylpyridinium chloride retention by the polysulphone membranes used during the ultrafiltration experiments was negatively affected by the presence of electrolytes and metal ions during preliminary investigations of both the palladium (ll) and platinum (lV) synthetic solutions. Though, it had already been observed that cetylpyridinium chloride was able to adsorb and effectively increase the hydrodynamic size of the Pt (lV) and Pd (ll) ions in aqueous solution as required during the micellisation process, it was also critical to keep the amount of the surfactant going to the waste stream at a minimal level in order to avoid further pollution of the waste stream by the surfactant. A series of experiments was conducted where the effect of electrolytes such as nitric acid, hydrochloric acid and sodium chloride were carefully studied in order to establish the optimum conditions required in order to achieve maximum retention of the surfactant.

4.2 Investigation of the effects of an electrolyte

In this section, an investigation of the cause of the deviating retention of the cetylpyridinium chloride in the presence of electrolytes such as hydrochloric acid, nitric acid and sodium chloride in synthetic solutions of the surfactant will be done. The content of cetylpyridinium chloride

57 solutions was kept constant at 10 mM in all the ultrafiltration experiments while increasing amounts of different electrolytes were added to the surfactant solutions. The choice of the concentration was based on the findings that were obtained in section 3.2.3. The results will be shown here in graphical form while the data can be found in tables in Appendix B.

4.2.1 Effect of hydrochloric acid concentration variation

The influence of hydrochloric acid addition on the CPC retention was investigated. This investigation was necessitated by the realisation in preliminary experiments in Chapter Three that CPC retention deviated significantly in the presence of metal ion solutions containing electrolytes. A set of cetylpyridinium chloride solutions of constant concentration (10 mM) was prepared by dissolving a suitable amount of CPC salt in deionised water in a 250 ml volumetric flask, with varying amounts of hydrochloric acid (ranging from 0 to 20 mM) added. Ultrafiltration runs were done at constant temperature (30oC) and pressure (150 kPa). Each ultrafiltration experiment was run for 20 minutes and at the end of each experiment, 20 ml permeate and retentate samples were taken for CPC analysis by UV-VIS

spectrophotometry. The results for this investigation are shown in Fig. 4.1 below with the data in Table B1 in Appendix B.

58

100.0

100.0

80.0

80.0 Permeate Flux (L/m2h)

CPC retention (%)

60.0

60.0

40.0

40.0

20.0

20.0

0.0 0.0 5.0 10.0 15.0 20.0

0.0 25.0

Hydrochloric acid concentration (mM) CPC retention Permeate flux

Figure 4.1: Variation of hydrochloric acid concentration at 30C, 150 kPa and 10 mM CPC

From the curves in Fig. 4.1 above, it can be seen that cetylpyridinium chloride retention decreased dramatically from just above 80% to less than 20% with increasing electrolyte (HCl) concentration ranging from 0 mM to 20 mM. The flux measurements showed a slight increase from approximately 60 L/m2h to just above 80 L/m2h at 0 mM to 5 mM acidic medium and remained fairly constant with increasing hydrochloric acid concentration.

In order to determine what changes in solution properties occur upon addition of hydrochloric acid, surface tension and viscosity

measurements were taken of solutions prepared in the same way as those used in the ultrafiltration runs and covering the acid concentration range used. Surface tension measurements were made manually using a tensiometer with torsion ring while viscosity measurements were made

59 with an Ostwald viscometer. This data is plotted as a function of acid concentration in Fig. 4.2.
0.045
surface tension

7.2
viscosity

surface tension (N/m )

0.044 0.043

7.15 7.1 7.05

0.042 7 0.041 0.04 0 5 10 15 [HCl] mM 20 25 6.95 6.9

Figure 4.2: Surface tension and viscosity of a 10 mM CPC solution as a function of HCl concentration

From the curves in Fig. 4.2 above, it can be seen that both cetylpyridinium chloride surface tension and viscosity decreased dramatically with the addition of hydrochloric acid and then reached a minimum value after 5 mM HCl was added. This can be explained in terms of surface effects, in the case of surface tension data, and effects in the bulk of the solution, in the case of viscosity measurements.

At 10 mM CPC the solution surface is already saturated with adsorbed monomers since the concentration of CPC exceeds the cmc value. Addition of chloride ions causes a screening effect of these ions on the positively charged head groups of the monomers. This allows the head groups which normally repel each other, to come closer together thus creating additional space at the surface for the adsorption of more monomers from the solution thereby decreasing the surface tension further, until a new saturation point is reached (in this case, around 5 mM HCl). The screening effect of the additional chloride ions on the micelles in the bulk of the solution is similar, allowing the head groups on

viscosity (N/m )

60 the micelle surface to come closer together thereby decreasing the ratio of the head group area to tail volume. If this effect occurs to a very large extent, that is, the ratio becomes lower than a certain critical value, the micelle can change its shape from a spherical to a more rod-like structure. This change is reflected in the abrupt viscosity change at around 5 mM HCl.

The abrupt changes in both the surface tension and viscosity at around 5 mM HCl could thus be indicating a saturation point and a change in micelle structure and could be the reason for the decreased retention of the surfactant solution. This abrupt change also corresponds with the point at which permeate flux reaches a maximum constant value (see Fig. 4.1).

4.2.2 Effect of nitric acid concentration variation

The influence of nitric acid addition on CPC retention was investigated. A set of cetylpyridinium chloride solutions of constant concentration (10 mM) was prepared by dissolving a suitable amount of CPC salt in deionised water in a 250 ml volumetric flask, with varying amounts of nitric acid (ranging from 0 to 20 mM) added. Ultrafiltration runs were done at constant temperature (30oC) and pressure (150 kPa). Each ultrafiltration experiment was run for 20 minutes and at the end of each experiment, 20 ml permeate and retentate samples were taken for CPC analysis by UV-VIS spectrophotometry. The results are shown in Fig. 4.3 with the data in Table B2 in Appendix B.

61

120.0 100.0 C P C r e te n ti o n (% ) 80.0 60.0 40.0 20.0 0.0 0.0 5.0 10.0 15.0 20.0

120.0 100.0 80.0 60.0 40.0 20.0 0.0 25.0 P e r m e a te F l u x (L / M 2 h )

Nitric acid concentration (mM) CPC retention Permeate flux

Figure 4.3: Variation of nitric acid concentration at 30C, 150 kPa and 10 mM CPC

A closer look at the curves in Fig. 4.3 show that hydrochloric acid and nitric acid behaved differently with respect to retention of cetylpyridinium chloride. With nitric acid variation, it can be seen that the retention of the surfactant eventually increased after an initial decrease, from nearly 80% to above 90% with increasing acid concentration, whereas flux measurements showed a dramatic decline from approximately 100 L/m2h to just above 40 L/m2h. It is evident that nitric acid concentration did not affect the micellisation process as much as hydrochloric acid, since the system was still able to achieve a high enough retention of the surfactant.

Surface tension measurements (see Fig. 4.4) show that compared with HCl, surface tension decreased continually with increasing HNO3 concentration and there was no abrupt change in the measurements over the concentration range measured. This could possibly be

62 explained as follows: although nitrate and chloride ions are both monovalent the nitrate ion has more electron lone pairs than the chloride ion thus providing a larger screening effect of the surfactant head groups which means that the surface saturation point of the additional surfactant molecules being adsorbed is reached at higher nitrate concentration.

0.045 0.044 0.043 0.042 0.041 0.04 0.039 0.038 0.037 0.036 0.035 0.034 0 5 10 15 [HNO3] mM

HNO3 HCl

surface tension (N/m )

20

25

Figure 4.4: Surface tension of a 10 mM CPC solution as a function of HNO3 concentration 4.2.3 Effect of sodium chloride concentration variation

The influence of sodium chloride addition on CPC retention was investigated. A set of cetylpyridinium chloride solutions of constant concentration (10 mM) was prepared by dissolving a suitable amount of CPC salt in deionised water in a 250 ml volumetric flask, with varying amounts of sodium chloride (ranging from 0 to 20 mM) added. Ultrafiltration runs were done at constant temperature (30oC) and pressure (150 kPa). Each ultrafiltration experiment was run for 20 minutes and at the end of each experiment, 20 ml permeate and retentate samples were taken for CPC analysis by UV-VIS

spectrophotometry. The results are shown in Fig. 4.5 below.

63

90.0 80.0

120.0 100.0

60.0 50.0

80.0 60.0

40.0 30.0 20.0 20.0 10.0 0.0 0.0 5.0 10.0 15.0 20.0 0.0 25.0 40.0

Sodium chloride concentration (mM) CPC retention Permeate flux

Figure 4.5: Study of variation of sodium chloride acid concentration at 30C, 150 kPa and 10 mM CPC

It is evident from Fig. 4.5 above that introduction of an electrolyte like sodium chloride failed to improve the retention of a surfactant, but in fact decreased it dramatically; a similar effect that was observed with hydrochloric acid addition. These results do not agree with the work of other researchers
3

who claim that introducing sodium chloride to

surfactant solutions reduces the critical micelle concentration leading to increased micellisation and increased retention. This is not the case here, and the results can be explained in the same way as for hydrochloric acid addition (section 4.2.1).

P e rm e a te F lu x (L /M 2 h )

C P C re te n tio n (% )

70.0

64 4.3 Summary of CPC retention investigations

Introduction of chloride ions reduces the surfactant retention significantly and the effect has been shown by viscosity and surface tension measurements to be probably due to a change in micelle structure.

Introduction of nitrate ions did not have a significant negative impact on the surfactant retention. This might be explained in terms of a second change in micelle structure .

It is concluded that the use of HCl to dissolve the metal salts should be kept to a minimum, thus the volume ratio of HNO3:HCl should be increased in the acid mixture used to dissolve Pt and Pd salts.

In order to shed further light on the reduced surfactant retention in the presence of electrolytes, the following chapter investigates the determination of the cmc value of cetylpyridinium chloride under various experimental conditions.

65

CHAPTER FIVE

THE CONCEPT OF MICELLISATION AND CONDUCTIVITY INVESTIGATIONS

In this chapter the focus will be on studying the extent to which micellisation occurred during the ultrafiltration experiments in the previous chapters. Conductivity studies will be used to confirm the theoretical cmc value of cetylpyridinium chloride and to determine the degree of ionisation of CPC in different media. The effects of various electrolytes namely, aqua regia, hydrochloric acid and nitric acid on the conductivity measurements of CPC solutions will also be investigated.

5.1 Micellisation

It

is

important

that

certain

conditions

namely,

critical

micelle

concentration (cmc), Kraft temperature point and the solubility of the surfactant are known in order to maximise the micellisation effect. The critical micelle concentration of a surfactant can be experimentally determined by employing a number of methods including, conductivity, surface tension measurements and capillary electrophoresis (CE).
29 13, 14,

These techniques can help to determine the extent or the degree to

which micellisation has occurred. It has been reported that the addition of an electrolyte such as sodium chloride to an aqueous solution containing the surfactant facilitates the reduction of the critical micelle concentration that in turn increases the micellisation process. 4

66 5.2 Conductivity study

In this study, a Metrohm 660 conductometer with conductivity cell (model no. 6.0908.110) coupled with a platinum thermocouple electrode was used to confirm and establish the influence of the following factors as listed below:

Determination and confirmation of the cmc value of CPC. Addition of varying amounts of different electrolyte(s) and synthetic mixtures containing either Na2PtCl6 or K2PdCl6 to cetylpyridinium chloride solutions to observe the effect of these on conductivity measurements.

5.2.1 Experimental determination of the cmc of CPC

This experiment was done in order to confirm the theoretical cmc value (0.9 mM) of cetylpyridinium chloride obtained from the literature. 3, 13 Of the various methods that can be employed namely, conductivity, surface tension and capillary electrophoresis, conductivity was chosen for this study due to the accessibility and simplicity of the equipment.

5.2.2 Experimental procedure

The conductometer was calibrated with 0.1 M KCl solution. After calibration, the cell constant of the conductivity cell at a specific temperature was calculated and other parameters and applicable settings of the conductometer were set prior to taking the conductivity measurements.

Cetylpyridium chloride solutions of varying concentrations (0.2 mM to 2 mM) were prepared by dissolving a calculated amount of CPC salt in deionized water and diluting this stock solution to the required concentration.

67

The conductivity measurements of the prepared CPC solutions were recorded as shown in Table C1, in Appendix C, and a plot showing the relationship between conductivity and CPC concentration is shown in Fig. 5.1 below:

180 160

conductivity (uS/cm)

140 120 100 80 60 40 20 0 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 R = 0.9966
2

R = 0.9956

Slope = 94 Slope = 43.36

[CPC] mM

Figure 5.1: Determination of the cmc of CPC and its degree of ionisation

The formation of the micelles leads to an abrupt change in conductivity of solution due to removal of ions from solution since the counter ions are adsorbed onto the micelle surface; thus the point at which the slope of the conductivity curve changes can be regarded as the onset of micellisation. Therefore the point of intersection of the two straight line portions of the plot in Fig. 5.1 is taken as the cmc value.

Looking at the curve in Fig. 5.1 above, it can be seen that the obtained cmc value is in agreement with the reported literature value (0.9 mM),
13 3,

thus the chosen technique and the methodology followed were

correct. The slopes of each plot in Fig. 5.1 above were also used to determine the degree of ionisation of the micelles as explained in section 5.2.3 below.

68

5.2.3 Determination of the degree of ionisation

The determination of the degree of ionisation of CPC micelles was done in order to investigate the available adsorption sites on the micelle surface. The degree of ionisation of a micelle was determined by measuring the change in slope of the solution electrical conductivity ( ) vs total concentration (C) as the solution goes through the cmc assuming the following conditions:

13, 28, 29

is only due to free chloride ions in solution

due to CP+ and micelles is negligible, thus

CCl

When C < cmc: = ACCl , since CPC monomer is fully ionised, where A = constant

When C > cmc, CCl = cmc +

(C cmc)

where

is the degree of ionisation of a micelle.

Thus

= A (cmc +

(C cmc))

Gradients follows:

above and below the cmc can be calculated as

dk/dC ( C > cmc ) = A

and

dk/dC ( C < cmc ) = A

Thus the ratio of these slopes gives , which is the degree of ionisation.

A closer look at Fig. 5.1 above also shows that the ratio of the two slopes, viz, 43.36 and 94.00, respectively, gives a 46% degree of ionisation. This means that 54% of the chloride counter ions are associated with the micelle surface or adsorbed onto the micelle surface.

69 5.3 Influence of electrolytes on the cmc value and degree of ionisation

Conductivity data is not useful when large amounts of acid are present in the surfactant solution because then the conductivity due to the acid is too high and small changes due to CPC are not observed, thus only small amounts of acid, to give a pH of around 3, were added to the CPC solutions. The results pertaining to this investigation are presented in graphical form below. 5.3.1 Determination of cmc in the presence of HCl

Surfactant solutions of various concentrations were prepared by dissolving calculated amounts of CPC salt in deionised water. HCl was added in the same volumetric flask (100 ml) prior to filling up to the mark with deionised water, to give a final concentration of 0.5 mM. The concentrations of the CPC solutions ranged from 0 mM to 2.2 mM. Conductivity measurements were made using a pre-calibrated (see section 5.2.1) Metrohm 660 conductivity meter. The conductivity meter measurements were plotted against CPC concentration in Fig. 5.2 and the data is given in Table C2 in Appendix C. The ratio of the two slopes was used to predict the degree of ionisation and the cmc value was also determined.

70

0.5

conductivity (mS/cm)

0.4

0.3

0.2

Slope = 0.2286 Slope = 0.098 Slope = 0.0369

0.1 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2

[CPC] mM
Figure 5.2: Plot of the conductivity vs CPC concentration in the presence of 0.5 mM HCl

A closer look at Figure 5.2 above shows that when a fixed amount of HCl is added to each CPC solution, conductivity measurements show three abrupt changes with the first cmc value occurring at around 0.25 mM CPC. This is in agreement with the accepted theory that electrolytes lower the cmc value of surfactants by reducing the head group area due to electrostatic screening of the head group charges by the additional counter ions. As a result of this, micellisation occurs sooner than it normally occurs at lower surfactant concentrations. A second cmc value occurs at around 1.2 mM CPC. This could indicate the point at which the spherical micelles transform into rod-shaped micelles with increasing surface area and corresponding greater degree of counter anion adsorption.

The degree of ionisation (obtained from the ratio of the two slopes in Fig. 5.1) is around 46% for CPC alone, but is reduced to 43% when HCl is added. The excess Cl ions in solution are now attracted to the charged micelles causing them to be removed from solution, thus leading to the abrupt change in conductivity, and the lower ionisation value. At the

71 second cmc value, the degree of ionisation is further reduced to 37.6% which shows that even more ions are associated with the micelle structure which now has a larger surface area.

5.3.2 Determination of cmc in the presence of Pd (ll) anions and aqua regia

CPC solutions were prepared in the same manner as described in 5.3.1 except that aliquots of the 1 mM Pd (ll) stock solution used for the preparation of the MEUF solutions were added to each solution, to give 0.01 mM concentration of Pd (ll), prior to making up to the mark with deionised water in the volumetric flasks (100 ml). The plot of solution conductivity against CPC concentration is shown in Fig. 5.3. The data is in Table C3 in Appendix C.
2 1.8

conductivity (mS/cm)

1.6 1.4 1.2 1 0.8 0.6 0 1 2 3 4 5 6 7 8 9

Slope = 0.0164 Slope = 0.5424 Slope = 0.1209

[CPC] mM
Figure 5.3: Plot of the Conductivity vs CPC concentration in the presence of 0.01 mM Pd (ll) anions in aqua regia

In the presence of Pd with aqua regia, the conductivity of increasing amounts of CPC showed interesting results. The first cmc value is not shown in Fig. 5.3 since it is out of the concentration range studied. (In acid medium we have seen that it occurs at around 0.2 mM CPC.) It can

72 be seen that there is a flattening off of the conductivity between 0.2 and 2 mM CPC indicating the adsorption of counter-ions onto the micelle surfaces. This is followed by an abrupt change in conductivity indicating a cmc value of around 2 mM. This could be the second cmc, the point at which the micelles could be changing shape. Between 2 and 3 mM CPC there is a sharp increase in conductivity. This could indicate a transition state where there is a change of structure. At around 3 mM there is another cmc value. The degree of ionisation i.e. the ratio of the two slopes around the cmc value of 3 mM is 22%. This value is considerably less than that of the micelles in the pure surfactant solution (46%) indicating that the palladium ions are adsorbed onto the micelle surface. 5.3.3 CMC determination in the presence of Pt (lV) anions and aqua regia

CPC solutions were prepared in the same manner as described in 5.3.1 except that aliquots of the 1 mM Pt (lV) stock solution used for the preparation of the MEUF solutions were added to each solution, to give 0.01 mM concentration of Pt (lV), prior to making up to the mark with deionised water in the volumetric flasks (100 ml). The plot of solution conductivity against CPC concentration is shown in Fig. 5.4. The data is in Table C4 in Appendix C.

73

1.6 1.5 1.4 1.3 1.2 1.1 1 0.9 0.8 0.7 0.6 0 1 2 3 4 5 6 7 8 9
Slope = 0.0376 Slope = 0.34 Slope = 0.0535

conductivity (mS/cm)

[CPC] mM
Figure 5.4: Plot of the conductivity vs CPC concentration in the presence of 0.01 mM Pt (lV) anions in aqua regia.

Looking at Fig 5.4 above, it can be seen that as was the case with Pd, two cmc values are observed. The first cmc value is close to 2 mM while the second cmc value is around 3 mM. The ratio of the two slopes around 3 mM CPC (0.0535/0.34) gives 15.7%. This value is less than that obtained for Pd (ll) (22%), indicating that there are fewer ions in solution i.e. more counter ions are associated with the micelle surface as can be observed from the flatter slope. This can mean that PtCl62- ions promote the transformation of the micelles to rod-shapes to a greater extent than PdCl42- ions with perhaps greater overall surface area leading to more elongated or longer rods.

74 5.4 Summary of the conductivity investigations

Findings on this research show that the presence of electrolytes lowers the initial cmc value of the surfactant and creates a second cmc value which possibly indicates a change in micelle shape or structure.

Also, it was found that the presence of the metal ions brings about a further change in conductivity through a third cmc value which could indicate a further possible change of micelle structure.

The ratios of the slopes around the cmc values give an indication of the degree of ionisation of the micelles and thus the amount of ions associated with the micelle surface.

The values of the slopes show that the Pt (IV) ions are absorbed to a greater extent than the Pd (II) ions onto the micelle surface.

75

CHAPTER SIX

IMPROVED CONDITIONS FOR THE RETENTION OF METAL ION AND SURFACTANT

In this chapter, a complete study of the optimum retention of both metal ions (Pt (lV) and Pd (ll)) and surfactant (CPC) will be investigated. Also the possibility of separating Pt (lV) from Pd (ll) will be explored. These investigations will be based on the findings obtained in the previous chapters that focused on establishing the reasons for the reduced retention of surfactant. The results for this chapter are illustrated in the form of graphs with the data contained in tables in Appendix D.

6.1 Micellar-enhanced ultrafiltration of individual metal ions

6.1.1 Ultrafiltration of platinum (lV) anions

Ultrafiltration of platinum metal ions alone as a function of metal ion concentration was done in order to determine the capability of the MEUF system to retain different amounts of metal from the synthetic solution. The synthetic solutions used for these experiments were prepared as follows:

A platinum stock solution was prepared by weighing a suitable amount of the metal ion salt as mentioned previously. The weighed salt was dissolved with a mixture of 2.5 mM HCl and 5 mM HNO3 and deionized water in a 500 ml volumetric flask. 2.5 mM HCl was the minimum amount of HCl that was necessary to dissolve PdCl62- salt and is considerably less than the amount in aqua regia.

76 Varying amounts of the metal solution were taken from the prepared stock solution to prepare the solutions for the ultrafiltration experiments and the appropriate amount of CPC was added as required by each ultrafiltration experiment.

Fig. 6.1 shows the retention of both Pt (lV) and CPC as well as the permeate flux as a function of metal ion concentration for experiments performed at 150 kPa, 30C and using 40 mM CPC. The data is found in Tables D1 and D2 in Appendix D.

100.0 99.0

100.0 80.0 60.0 40.0 20.0 0.0 0.50 P e r m e a t e F lu x ( L /m 2 h r )

98.0 R e te n tio n (% ) 97.0 96.0 95.0 94.0 93.0 92.0 0.00 0.10 0.20 0.30 0.40

Pt concentration (mM)
Pt retention CPC retention Flux variation

Figure 6.1: MEUF of Pt (lV) anions at 40 mM CPC, 30C, and 150 kPa in acidic medium

From the curves in Fig. 6.1 above, it can be seen that the retention of Pt (lV) was between 98% and 100% with a slight increase observed as initial Pt (lV) concentration in the solution increased. The CPC retention was 99% at low metal concentration and decreased to around 93% at

77 higher metal concentration. The higher retention can be attributed to sufficiently large micelles which form at 40 mM CPC and a low enough electrolyte concentration to prevent the electrolyte effect that was discussed in the previous chapter. However, the slight decrease in CPC retention observed with increasing Pt (lV) concentration can be attributed once again to a slight electrolyte effect, since the higher metal concentration solutions also contained proportionately more electrolytes. The flux measurements decreased slightly from just above 45 L/m2h and remained fairly constant with increasing metal ion concentration (0 to 0.4 mM) at constant surfactant concentration (40 mM). This slight decline in flux measurements can be attributed to concentration polarization on the membrane surface that occurs increasingly with increasing metal ion concentration.

6.1.2 Ultrafiltration of Palladium (ll) anions

Ultrafiltration of palladium metal ion alone was done in order to determine the capability of the MEUF system to retain the metal from the synthetic solution with increasing palladium concentration. Palladium synthetic solutions used in these ultrafiltration experiments were prepared exactly in the same manner as described in section 6.1.1 above.

Fig. 6.2 shows the retention of both Pd (ll) and CPC, as well as the permeate flux as a function of metal ion concentration for experiments performed at 40 mM CPC, 150 kPa and 30C. The data is found in Tables D3 and D4 in Appendix D.

78

102.0 100.0 m e ta l i o n r e te n ti o n (% ) 98.0

100.0 80.0 P e r m e a te F l u x (L / M 2 h )

60.0 96.0 40.0 94.0 92.0 90.0 0.00 20.0 0.0 0.50

0.10

0.20

0.30

0.40

Pd concentration (mM) Pd retention CPC retention Permeate flux

Figure 6.2: MEUF of Pd (ll) anions at 40 mM CPC, 30C, and 150 kPa in acidic medium

Looking at the curves of the palladium-cetylpyridinium chloride system in Fig. 6.2, it is evident that Pd (II) was retained at 100% irrespective of the initial Pd (II) concentration. However, it was also observed that the retention of cetylpyridinium chloride gradually decreased from 98 to 90% with increasing metal ion concentration. Although the overall surfactant retention was high, the slight decrease would be due to increasing electrolyte concentration as metal ion concentration increases. Also, it was found that flux measurements decreased slightly initially and later remained fairly constant with increasing palladium concentration from 0 to 0.4 mM, as was found with Pt (lV) ultrafiltration experiments.

79 6.2 Micellar-enhanced ultrafiltration Pt (lV)-Pd (ll) mixture

The possibility of separating the two metal ions in an acidic synthetic mixture containing varying ratios (1:1 to 1:6) of the two metal ions, was investigated. The total metal concentration of the synthetic mixture was kept constant at 1 mM throughout, while the ratios of the metal ions were varied. Table 6.1 shows the exact metal ion ratios that were used in these ultrafiltration experiments. Table 6.1: Summary of varying metal ion concentration ratios Metal ion ratio Exact *MA concentration (mM) 1:1 1:2 1:3 1:4 1:6 0.05 0.0333 0.025 0.02 0.015 0.05 0.0666 0.075 0.08 0.085 Exact *MB concentration (mM)

*Can be any of the two metal ions, that is Pt or Pd

Fig. 6.3 shows the micellar-enhanced ultrafiltration of Pt (lV)/Pd (ll) mixture in acidic medium when Pd (ll) concentration ratio is kept constant. The data is found in Table D7 in Appendix D.

80
99.0 98.0 97.0 96.0 95.0 94.0 93.0 92.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0

metal ion retention (%)

metal ion ratio (1 : x) Pt retention Pd retention

(1 = constant Pd concentration ratio, x = changing Pt concentration ratio) Figure 6.3: MEUF of a mixture of Pd (ll) - Pt (lV) anions at 40 mM CPC, 30C, and 150 kPa in acidic medium

Pt (lV) anion retention increases sharply initially until it reaches 98% at Pd:Pt ratio of 1:2 and later decreases to below 96% at Pd:Pt ratio of 1:4 ratios and increases again to 98% at Pd:Pt ratio of 1:6. Pd (ll) retention follows the same trend as well but at an overall lower retention. This difference in metal ion retention shows that there is competition between the two metal ions for available sites on the surfactant surface with the platinum ions being preferentially adsorbed onto the micelles. In each of these solutions except the 1 : 1 ratio, the concentration of platinum ions is greater than that of palladium ions, hence the separation factor increases with increased platinum concentration.

Fig. 6.4 shows the micellar-enhanced ultrafiltration of Pt (lV)/Pd (ll) mixture in acidic medium when Pt (lV) concentration ratio is kept constant and the amount of palladium relative to platinum is increasing. The data is found in Table D8 in Appendix D.

81

100.0 M e ta l i o n r e te n ti o n (% ) 99.0 98.0 97.0 96.0 95.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0

metal ion ratio (1 : x) Pt retention Pd retention

(1 = constant Pt concentration ratio, x = changing Pd concentration ratio) Figure 6.4: MEUF of a mixture of Pt (lV)-Pd (ll) anions at 40 mM CPC, 30C, and 150 kPa in acidic medium

Looking at Fig. 6.4 above, it is evident that palladium retention increases steadily from just above 96% to nearly 99% with increasing metal ion concentration ratio (Pt: Pd), that is, with more Pd (ll) present in the system compared to Pt (lV) , the Pd (ll) is increasingly retained whilst platinum retention decreases slightly from 98% to 97% in the same metal ion concentration ratio region (1:1 to 1:3). Also, it was observed that the retention of the two metal ions increased slightly again beyond 1:4 Pt:Pd concentration ratio with platinum achieving more than 99.5% while palladium retention remained below 98%. The variation in retention of the two metal ions can be attributed to the differing adsorbing capabilities that they have towards the available charged adsorbing sites on the surfactant surface. However, the differences remain very small.

82 6.3 Membrane response during Pt/Pd mixture ultrafiltration

Membrane response during the micellar-enhanced ultrafiltration of the mixture of Pt (lV) and Pd (ll) was carefully monitored by monitoring the cetylpyridinium chloride retention and permeate flux variation.

6.3.1 CPC retention

The curves in Fig. 6.5 below were constructed from the sample analysis data that was obtained during the ultrafiltration experiments of the Pt/Pd synthetic mixtures. The samples were analysed for CPC content by UVVIS spectrophotometry. The data pertaining to this investigation can be obtained in Tables D5 and D6 in Appendix D.

94.0

93.0

92.0 CPC retention (%)

91.0

90.0

89.0

88.0 0.0 1.0 2.0 3.0 4.0 metal ion ratio 5.0 6.0 7.0

CPC retention when Pt ratio is constant CPC retention when Pd ratio is constant

Figure 6.5: Effects of metal ion ratio on CPC retention in acidic medium in the presence of various mol ratios of Pd and Pt

83 In the presence of fixed Pd (ll) in the metal ion concentration range of 1:1 to 1:4 Pd : Pt, it can be seen that CPC retention decreased sharply from just above 92% to just above 88%, while in the same region of metal ion ratio in the presence of constant Pt (lV), CPC retention slightly increased initially from just above 92% to close to 94% and later decreased and followed the same trend as in the case where Pd (ll) concentration was kept constant. For the two metal ions above 1:4 metal ratios, CPC retention increased sharply from as low as 88% to nearly 92%. However, though the CPC retention was affected by the changing metal ion ratio, the system where Pt (lV) ratio was kept constant was the most affected as it only achieved a maximum of just more than 92% while in the system where Pd (ll) ratio was kept constant close to 94% retention of CPC was achieved. The electrolyte content is constant in these experiments since the total metal ion concentration was held constant. The only change is the relative amounts of Pd (ll) and Pt (lV). It is then evident that the metal ions themselves influence the shapes of the micelles due their large sizes and need for a larger surface area. The PtCl62- anion has a larger effect on the micelle structure than the PdCl42as can be seen from the lower retention of CPC when there are more Pt (lV) ions relative to Pd (ll) ions. 6.3.2 Flux variation

The curves in Fig. 6.6 are constructed from the sample analysis data that was obtained during the ultrafiltration runs of Pt/Pd synthetic mixtures. The data is found in Tables D7 and D8 in Appendix D.

A closer look at the curves in Fig. 6.6 shows that for both systems, thus when either Pt : Pd = 1 : x or Pd : Pt = 1 : x, the flux measurements continually decreased throughout. However, although the flux variations in both systems followed the same trend, flux measurements for the Pd : Pt =1 : x system were still higher than in the system of Pt : Pd = 1 : x.

84

50.0 P e rm e a te F lu x v a riatio n (L /M 2 h )

40.0

30.0

20.0

10.0

0.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 metal ion ratio (mM) Permeate flux when Pt concentration ratio is constant Permeate flux when Pd concentration ratio is constant

Figure 6.6: Flux variation during Pt(lV)/Pd (lV) ultrafiltration

The differences in flux measurements can be attributed to the manner in which these two metal ions adsorb on the available oppositely charged sites of the surfactant surface. The slight decrease in flux measurements can also be due to different ratios of the metal ion and the way that they influence a micelle shape which influences flux.

6.4 Summary of the investigation of improved conditions

The conditions for improved micellisation to occur in this investigation lead to the use of 40 mM of the CPC surfactant, a pressure of 150 kPa, and a temperature of 30C.

It was also found that controlling or minimizing the electrolyte content, especially chloride content, led to optimum retention of both the metal ion(s) and the surfactant.

Quantitative separation of the two metal ions under these conditions could, however, not be achieved.

85

CHAPTER SEVEN

CONCLUSIONS

7.1 Conclusion

Based on the findings of this study, it can be concluded that the MEUF system using cetylpyridinium chloride (CPC) can be used to recover or retain Pt (lV) and Pd (ll) anions from industrial waste effluents. It can also be said that PtCl62- due to its greater adsorption capabilities onto the micelle surface than PdCl42- or PdCl3 (H2O)- was preferentially retained in neutral medium. This may be exploited as a possible means of separating the two metal ions.

However, although the system was able to achieve optimum retention of both metal ions, the CPC retention was very poor during initial investigations. This was attributed to the electrolyte effect which influences the micellisation process, possibly changing the shape or structure of the micelles. These findings necessitated the investigation of suitable experimental conditions that would permit the optimum retention of both the metal ion(s) and the surfactant. The study considered the influence of different electrolytes on the physical properties of CPC solutions to establish the conditions under which surfactant retention was a maximum.

The conditions which were found for optimum micellisation to occur in this investigation lead to the use of 40 mM of the CPC surfactant, 150 kPa, and 30C. It was also found that controlling or minimizing the electrolyte content led to optimum retention of both the metal ion(s) and the surfactant.

86 7.2 Recommendations

Continued investigation of this project could be carried out, viz.: Investigation of the capability of a different membrane that would provide different specifications namely MWCO and membrane pore size. Using a different cationic surfactant with different properties that may not be as sensitive to electrolyte effects. Investigating the retention of other platinum group metals. Focusing on the separation of Pt (lV) and Pd (ll) by incorporating into the surfactant micelles a specific separating agent such as an alkylpyrazole, for example, which is known to be Pd (ll) specific.

87

REFERENCES
1. Thomas M.P. (2000). The Utilization of toxic paint waste generated in the automotive industry as a low-grade fuel in the cement manufacturing Industry. M Tech Thesis, Port Elizabeth Technikon. (pp 1-11) 2. Bennen W. (2002).The evaluation of waste minimization/waste treatment strategies for a commercial production process of 4methyl-3-thiosemicarbazide. Technikon. (pp 1-13) 3. 4. Gzara L. Dhahbi M., (2000). Desalination, 137: 241 - 250 Juang R.S., Xu Y.Y., Chen C.L., (2003). Desalination, 218: 257 267 5. 6. 7. 8. www.webelements.com/Pt Cowey A., Mining and metallurgy in South Africa. Mintek, 1994 Hartley F.R. Chemistry of Platinum Group Metals. Elsevier, 1991. Vogts S.E., (2004). The separation of Palladium and Platinum from hydrochloric acid medium. PhD. Thesis, University of Port Elizabeth. (pp 1 - 30) 9. Rao C.R.M., Reddi G.S., (2000). Trends in Analytical Chemistry: 19 (9), 565 - 585 10. Louw T., (2004). The development and application of platinum selective separating agents. MSc. Thesis, University of Port Elizabeth. (pp 1 - 35) 11. Viviers C., (1995). Facets of Rhodium and Iridium separation. PhD Thesis, University of Port Elizabeth. (pp 1 -36) 12. www.google.com/platinum, encyclopedia. 13. Pashley M.R., Karaman E.M., Applied Colloid and Surface Chemistry, J. Wiley and Sons, England, 2004. 14. www.kcpc.usyd.edu.au/discovery 15. www. petrosepmembrane.com/membranes 16. Ullmans Encyclopedia of Industrial Chemistry, A16, pp 187 - 264 Platinum-Wikipedia, The free M Tech Thesis, Port Elizabeth

88 17. Filtration and Ultrafiltration Techniques:

http//membranes.nist.gov.com 18. Jacobs E. P., Fane T. (2003). Shortcourse on Introduction to membrane science and technology presented at P.E. Technikon. 19. Zydney A., (2005). Workshop on Membranes for Liquid

Separations, Including Fouling Issues (MF,UF,NF,RO) presented at International Congress on Membranes and Membrane

Processes. Seoul, Korea. 20. Twitchell J., (2000). What is Ultrafiltration?. www.dost.gov.ph, 20051003. 21. Baek K., Lee H.H., Yang J.W., (2003). Desalination, 158:157 - 166 22. Mtyopo B.M., (2004). Optimisation of a manufacturing process for Atrazine with a focus on waste minimization. M Tech Thesis, Port Elizabeth Technikon. (pp 35 36) 23. Zeelie B., Laboratory Process Development. 2003, pp 60 - 66 24. Holler F. J., Skoog D.A., West D.M. Fundamentals of Analytical Chemistry 7th Edition, Saunders College Publishers, New York, 1991. 25. Konkel J. Analytical Chemistry for Technicians, Lewis Publisher Inc. Lincoln Nebraska, 1991. 26. Beamish F.E. The Analytical Chemistry of Noble Metals, Pergamon,Oxford, 1966. 27. Swart P., Maartens A., Engelbrecht J., Jacobs E.P.(1999). The Development and Implementation of Biological Cleaning

Techniques for Ultrafiltration and Reverse Osmosis Membranes fouled by Organic Substances. WRC Report No 660/1/99. 28. Attwood D., Florence A.T., Surfactant systems: Their chemistry, pharmacy and biology. Chapman and Hall, London, 1983. 29. Everett D.H., Basic Principles of Colloid Science . Royal Society of Chemistry, 1988. 30. Hunter R.J. Introduction to modern colloid science. Oxford University Press Inc., New York, 1993. 31. Zeelie B. (1996). Iodo Complexes. MSc Thesis, University of Port Elizabeth. (pp 12-14)

89

APPENDIX A
Preliminary investigations of metal ion and surfactant retention

Table A1: CPC calibration curve

CPC (mM) 0.00098 0.00196 0.00392 0.0049 0.0098 0.0196 0.0392 0.098 0.196 Absorbance 0.0048 0.01 0.0191 0.0232 0.0452 0.0948 0.175 0.424 0.8182

Table A2: Effect of pressure variation Table A2 (1): CPC data

Experiment number #1 [CPC]I (mM) 10 10 10 10 10 #2 10 10 10 10 10 Pressure (kPa) 50 100 150 200 250 50 100 150 200 250 CPC concentration (mM) Feed 9.755 9.958 9.921 9.949 9.919 9.968 10.086 9.769 9.846 9.824 Permeate 0.549 0.854 1.287 2.763 4.543 0.521 0.823 1.194 2.990 4.733

90 Table A2 (2): Averaged data: Effect of pressure variation

[CPC] (mM) 10 10 10 10 10 Pressure (kPa) 50 100 150 200 250 #1 69.28 99.03 120.82 141.07 107.04 Flux (L/m h) #2 69.03 95.17 119.39 138.78 106.02 Av 69.16 97.09 120.10 139.92 106.53 #1 94.37 91.42 87.03 72.23 54.20
2

% CPC Retention #2 94.78 91.84 87.78 69.63 51.82 Av 94.58 91.63 87.41 70.93 53.01

Table A3: Effect of temperature variation

[CPC] (mM) 10 10 10 10 10 Temperature C 10 20 30 40 50 Flux (L/m h) 184.04 160.98 107.05 93.98 83.12
2

CPC concentration (mM) Feed 9.96 10.10 9.91 10.02 9.48 Permeate 7.81 7.40 1.73 3.50 3.98

Retention % 21.61 26.79 82.60 65.08 57.97

91 Table A4: CPC concentration variation

Experiment number #1 [CPC]i (mM) 0 2.5 5.0 7.5 10 12.5 15.0 25 45 #2 0 2.5 5.0 7.5 10 12.5 15.0 25 45 Flux (L/m h) 103.58 146.28 146.28 146.28 136.08 80.67 66.79 53.83 49.90 103.58 147.91 98.01 85.82 82.35 80.67 66.28 53.829 49.900
2

CPC concentration (mM) Feed 10.178 2.448 4.950 7.565 10.163 13.875 14.909 23.830 45.054 10.178 2.662 5.400 7.769 10.001 13.875 15.734 23.830 45.054 Permeate 1.754 0.618 1.029 0.832 1.075 1.413 1.562 1.238 1.554 1.754 0.872 1.255 1.311 1.628 1.413 1.282 1.238 1.554

Retention % 82.77 74.77 79.22 89.00 89.42 89.82 89.52 94.80 96.55 82.77 67.24 76.76 83.12 83.72 89.82 91.85 94.80 96.55

92 Table A5: Pd ultrafiltration in varying CPC concentration in acidic medium

[Metal] mM 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 [CPC] mM 1 2 3 4 5 10 20 40 60 80 100 Pd concentration (ppm) Experiment # 1 F* 7.307 7.587 6.236 7.726 8.109 7.806 7.826 7.378 9.641 8.111 9.774 R* 1.015 2.302 1.469 2.746 1.99 4.304 4.509 7.853 8.452 8.806 9.459 P* 0.089 0.255 0.075 0.177 0.735 3.623 1.812 1.419 0.509 1.011 0.726 F* 7.307 7.587 6.236 7.726 8.109 7.813 8.898 9.569 10.026 8.834 7.307 Pd concentration (ppm) Experiment # 2 R* 1.015 2.302 1.469 2.746 1.99 9.146 10.147 9.888 16.576 10.23 1.0156 P* 0.089 0.255 0.075 0.177 0.735 0.347 0.257 0.014 1.051 0.945 0.089

*F = Feed concentration, R = Retentate concentration, P = Permeate concentration

Table A6: Averaged data of Pt and Pd ultrafiltration with varying CPC concentration in acidic medium
[Metal] mM 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 [CPC] mM 1 2 3 4 5 10 15 20 30 40 Platinum-CPC system % Retention Pt 98.85 98.79 98.87 98.56 98.25 98.06 97.59 95.84 95.66 94.41 CPC 59.43 41.86 31.94 24.64 21.60 18.26 15.14 18.21 18.75 7.63 Palladium-CPC system % Retention Pd 98.78 98.46 99.53 97.98 97.10 97.77 96.38 97.45 96.13 95.52 CPC 56.28 36.30 33.63 31.10 35.28 30.60 29.61 43.68 35.21 42.16

93 Table A7: Pt ultrafiltration with varying CPC concentration in neutral medium

[Metal] mM 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 [CPC] mM 1 2 3 4 5 10 20 40 60 80 100 Pt concentration (ppm) Experiment # 1 F 14.23 14.69 16.85 17.85 17.59 23.99 24.51 19.16 18.39 19.31 18.25 R 4.34 3.62 4.17 4.74 6.54 0.27 3.06 16.19 13.34 14.98 17.11 P 0.133 0.201 0.226 0.289 0.297 0.766 0.196 0.658 0.704 0.650 0.683 F 14.23 14.69 16.85 17.85 17.59 22.61 21.75 21.22 19.77 20.7 14.23 Pt concentration (ppm) Experiment # 2 R 4.343 3.623 4.171 4.74 6.54 15.72 13.77 13.84 10.87 9.497 4.343 P 0.132 0.201 0.226 0.289 0.297 0.534 0.741 0.689 1.291 1.078 0.132

Table A8: Pd ultrafiltration with varying CPC concentration in neutral medium

[Metal] mM 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 [CPC] mM 1 2 3 4 5 10 20 40 60 80 100 Pd concentration (ppm) Experiment # 1 F 7.307 7.587 6.236 7.726 8.109 7.806 7.826 7.378 9.641 8.111 9.774 R 1.016 2.302 1.469 2.746 1.990 4.304 4.509 7.853 8.452 8.806 9.459 P 0.089 0.256 0.076 0.177 0.736 3.623 1.812 1.419 0.509 1.011 0.726 F 7.307 7.587 6.236 7.726 8.109 7.813 8.898 9.569 10.026 8.834 7.307 Pd concentration (ppm) Experiment # 2 R 1.016 2.302 1.469 2.746 1.990 9.146 10.147 9.888 16.576 10.230 1.016 P 0.089 0.256 0.076 0.177 0.736 0.348 0.258 0.014 1.051 0.945 0.089

94 Table A9: Averaged data of Pt and Pd ultrafiltration with varying CPC concentration in neutral medium
[Metal] (mM) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 [CPC] (mM) 1 2 4 5 10 40 60 80 100 Metal ion- CPC sytem % Retention Pt 99.07 98.63 98.38 98.31 97.26 96.66 96.17 95.52 95.05 Pd 98.88 98.79 97.70 95.55 90.31 89.52 89.30 98.88 98.79

Table A10: Separation study of Pt/Pd mixture in acidic medium

[Metal] mM 0.1 0.1 0.1 0.1 0.1 [CPC] mM 10 20 40 80 100 Pd concentration (ppm) F 11.14 10.10 10.58 10.25 10.53 R 2.08 5.83 6.49 8.10 8.47 P 0.44 0.53 2.09 2.61 2.35 F 20.64 19.91 20.60 18.55 20.28 Pt concentration (ppm) R 4.24 12.33 11.40 13.42 14.29 P 0.44 0.42 0.66 0.99 0.58 % Retention Pt 97.86 97.88 96.77 94.65 97.12 Pd 96.03 94.76 80.28 74.55 77.72

95 Table A11: Effect of an electrolyte in metal ion and surfactant retention Palladium-cetylpyridinium chloride-sodium chloride system
[Metal] mM 0.1 0.1 0.1 0.1 0.1 [NaCl] mM 0 10.00 25.00 50.00 100.00 F 41.13 36.03 39.64 38.68 [CPC] mM P 4.61 7.18 8.89 21.83 F Palladium concentration (ppm) R P % Retention Pd 90.31 85.79 84.95 84.46 84.20 CPC 93.34 88.79 80.07 77.58 43.56

8.307 6.482 4.849 6.710

6.724 5.139 4.288 3.627

0.357 0.437 0.752 1.044

Platinum-cetylpyridinium chloride-sodium chloride system

[Metal] mM 0.1 0.1 0.1 0.1 0.1 [NaCl] mM 0 10.00 25.00 50.00 100.00 F 37.64 40.70 44.23 44.13 [CPC] mM P 27.51 35.83 41.70 41.66 F Platinum concentration (ppm) R P % Retention Pt 96.66 95.05 95.86 95.24 94.15 CPC 38.37 27.59 12.03 5.73 5.55

15.21 15.27 16.15 13.40

11.69 12.43 8.12 4.90

0.69 0.57 0.76 0.77

96 Table A 12: Flux variation with CPC concentration in various experimental conditions (Membrane response)
Experiment CPC (mM) 10 20 CPC alone 40 80 100 10 20 CPC + Pd 40 80 100 10 20 CPC + Pt 40 80 100 10 20 Pd + Pt 40 80 100 96.05 48.11 37.62 25.70 25.45 126.90 60.41 54.49 33.88 27.95 89.99 49.54 36.48 29.95 28.72 122.05 63.22 47.29 34.28 24.59 Flux (L/m h) Batch # 1 Batch # 2 Average 62.75 57.91 39.64 27.7 27.43 93.02 48.83 37.05 27.83 27.09 124.48 61.82 50.89 34.08 26.27 60.03 58.01 51.89 38.87 36.33
2

Table A 13: Flux measurements after ultrafiltration of various species

Time (minutes) 20 40 60 80 100 Original 94.14 94.14 94.14 94.14 94.14 After CPC 74.19 74.16 74.15 74.13 74.12 Flux (L/m2h) After Pd 64.19 64.20 64.20 64.20 64.20 After Pt 70.21 70.20 70.20 70.20 70.20 After backflush 94.19 94.19 94.19 94.19 94.19

97

APPENDIX B
Investigation of cetylpyridinium chloride retention

Table B1: Variation of hydrochloric acid concentration

Experiment number [HCL] mM 0 Flux (L/m h) 66.839 86.330 86.636 86.687 86.738 66.890 86.228 86.330 86.432 86.636
2

CPC concentration (mM) Feed 10.178 10.123 9.999 10.039 10.118 10.178 10.316 10.236 10.300 10.241 Permeate 1.754 2.981 5.060 7.078 8.210 1.754 4.183 5.693 6.525 8.241

Retention % 82.77 70.55 49.39 29.49 18.86 82.77 59.45 44.38 36.65 19.53

#1

5 10 15 20 0 5

#2

10 15 20

Table B2: Variation of nitric acid concentration

Experiment number [HNO3] mM 0 Flux (L/m h) 103.576 84.850 70.819 70.666 49.951 106.484 88.830 76.279 69.646 49.237 106.484 84.29 71.43 67.40 50.10
2

CPC concentration (mM) Feed 10.178 9.795 10.261 10.254 10.297 10.178 10.427 10.591 10.304 10.147 10.178 9.518 9.461 9.654 9.759 Permeate 1.754 4.131 3.097 1.691 1.497 1.754 3.780 3.368 1.812 1.537 1.754 3.886 2.078 1.567 1.236

Retention % 82.77 57.83 69.81 83.50 85.46 82.77 63.75 68.20 82.42 84.85 82.77 59.169 78.034 83.767 87.331

#1

5 10 15 20 0 5

#2

10 15 20 0 5 10

#3

15 20

98 Table B3: Variation of sodium chloride concentration

Experiment number [NaCl] mM 0 2.5 5.0 Flux (L/m h) 102.20 55.51 53.01 51.84 51.18 50.61 65.77 107.30 60.67 56.84 52.50 51.69 51.43 65.77 107.30 64.75 63.73 88.37 63.32 62.71 65.77 107.30 98.07 88.83 88.37 84.49 82.40 80.82
2

CPC concentration (mM) Feed 11.293 9.849 9.653 9.792 9.806 10.503 9.666 10.519 10.560 10.305 10.528 10.464 10.503 9.666 10.519 10.570 9.849 9.789 9.797 9.796 9.666 10.519 9.844 9.773 9.789 9.525 9.637 9.581 Permeate 1.754 6.917 7.058 7.093 7.500 8.034 6.710 1.799 4.418 4.618 5.014 5.467 7.845 6.710 1.799 5.565 4.217 4.969 7.066 4.126 6.710 1.799 3.121 5.551 4.969 5.788 7.402 7.465

Retention % 84.47 29.77 26.89 27.57 23.51 23.51 30.58 82.89 58.16 55.18 52.37 47.76 25.31 30.58 82.89 47.35 57.18 49.24 27.87 57.88 30.58 82.89 68.29 43.20 49.24 39.24 23.20 22.09

#1

7.5 10.0 15 20 0 2.5 5.0

#2

7.5 10.0 15 20 0 2.5 5.0

#3

7.5 10.0 15 20 0 2.5 5.0

#4

7.5 10.0 15 20

99

APPENDIX C
Conductivity studies

Table C1: Determination of the cmc of CPC

cell constant = [CPC] mM 0.2 0.4 0.6 0.8 1 1.2 1.4 1.8 2

0.9365 Temp C 28.4 28.4 28.5 28.5 28.4 28.4 28.2 28.3 28.2 0.461

conductivity S/cm 37.3 55.7 77.2 92.8 109.6 121 129.6 145 154.4

degree of ionisation =

Table C2: Determination of the cmc of CPC in the presence of 0.5 mM HCl
[CPC] mM 0 0.16 0.24 0.32 0.4 0.48 0.56 0.64 0.8 1 1.2 1.4 1.6 1.8 2 Conductivity mS/cm 0.294 0.33 0.349 0.357 0.3645 0.3725 0.3815 0.391 0.4025 0.4225 0.446 0.462 0.4565 0.4705 0.491

100 Table C3: Determination of cmc of CPC in the presence of Pd and aqua regia
[CPC] mM 0.2 0.4 0.6 0.8 1 1.2 1.4 1.8 2 2.4 2.8 3 3.5 4 4.5 5 6 7 8 conductivity mS/cm 1.04 0.812 0.82 0.83 0.83 0.83 0.84 0.84 0.84 1.19 1.34 1.39 1.49 1.44 1.57 1.65 1.9 1.93 1.92

Table C4: Determination of cmc of CPC in the presence of Pt and aqua regia
[CPC] mM 0.2 0.4 0.6 0.8 1 1.2 1.4 1.8 2 2.4 2.8 3 3.5 4 4.5 5 6 7 8 conductivity mS/cm 1.333 0.72 0.819 0.867 0.869 0.87 0.873 0.879 0.832 0.975 1.104 1.114 1.125 1.129 1.136 1.237 1.252 1.339 1.345

101

APPENDIX D
Improved experimental conditions for the metal ion and surfactant retention

MEUF of Pt (lV) anions in acidic medium Table D1: CPC data

Sample no. Averaged absorbance Feed 1 2 3 4 5 0.9709 0.9805 0.9939 1.0895 1.0261 Permeate 0.0201 0.0208 0.0787 0.1310 0.1416 CPC concentration (mM) Feed 46.025 46.480 47.115 51.647 48.642 Permeate 0.477 0.493 1.865 3.105 3.357 Retention % 98.96 98.94 96.04 93.99 93.10

Table D2: Metal ion data

Metal ion concentration Sample no. Feed 1 2 3 4 5 0.0332 0.0869 0.1354 0.1902 0.2557 (mM) Permeate 0.0008 0.0014 0.0021 0.0012 0.0012 Flux (L/m h) 48.60 43.70 38.90 36.24 35.63
2

Retention % 97.73 98.38 98.48 99.40 99.55

MEUF of Pd (ll) anions in acidic medium Table D3: CPC data

Sample no. Averaged absorbance Feed 1 2 3 4 5 1.0293 0.9945 0.9927 0.9923 0.9242 Permeate 0.0394 0.0493 0.0721 0.0914 0.1755 CPC concentration (mM) Feed 48.794 47.144 47.059 47.040 43.811 Permeate 0.933 1.168 1.708 2.165 4.160 Retention % 98.09 97.52 96.37 95.40 90.51

102 Table D4: Metal ion data

Metal ion concentration Sample no. Feed 1 2 3 4 5 0.0237 0.0354 0.0350 0.0636 0.1712 (mM) Permeate 3.4E-05 4.6E-05 9.8E-06 1.6E-05 2.4E-05 Flux (L/m h) 45.18 31.90 31.14 30.07 29.56
2

Retention % 99.86 99.87 99.97 99.97 99.99

Pt/Pd mixture ultrafiltration in acidic medium Table D5: CPC data obtained when [Pt] : [Pd] = 1 : x
Metal ion ratio Pt : Pd 1:1 1:2 1:3 1:4 1:6 Averaged absorbance Feed 0.9963 0.9863 1.0023 0.9819 0.9919 Permeate 0.1564 0.1312 0.1353 0.1753 0.1603 CPC concentration (mM) Feed 47.229 46.755 47.514 46.547 47.021 Permeate 3.707 3.110 3.207 4.155 3.799 Retention % 92.15 93.35 93.25 91.07 91.92

Table D6: CPC data obtained when [Pd] : [Pt] = 1 : x

Metal ion ratio Pd : Pt 1:1 1:2 1:3 1:4 1:6 Averaged absorbance Feed 1.0212 1.0166 1.0062 0.9202 1.0302 Permeate 0.1582 0.1627 0.1847 0.2031 0.1672 CPC concentration (mM) Feed 48.410 48.192 47.699 43.622 48.836 Permeate 3.750 3.856 4.378 4.814 3.963 Retention % 92.25 92.00 90.82 88.96 91.89

103 Table D7: Metal ion data when [Pd] : [Pt] = 1 : x

Ratio Flux (L/m2h) 28.84 27.77 25.27 22.15 20.67 [Platinum] (mM) F 0.05 0.0666 0.075 0.08 0.085 P 4.8E-04 3.8E-04 5.6E-04 9.8E-04 5.7E-04 F 0.05 0.0333 0.025 0.02 0.015 [Palladium] (mM) P 9.5E-04 3.5E-04 2.9E-04 5.3E-04 5.2E-04 Pt 96.6 98.2 97.3 95.8 98.3 Retention % Pd 93.3 96.9 95.1 92.4 94.1

1:1 1:2 1:3 1:4 1:6

Table D8: Metal ion data when [Pt] : [Pd] = 1 : x

Ratio Flux (L/m2h) 40.17 38.44 35.48 29.66 25.42 [Platinum] (mM) F 0.05 0.033 0.025 0.02 0.015 P 4.6E-04 3.5E-04 3.1E-04 3.6E-04 4.3E-04 F 0.05 0.0666 0.075 0.08 0.085 [Palladium] (mM) P 4.7E-04 2.5E-04 2.0E-04 5.0E-04 4.3E-04 Pt 98.1 97.8 97.1 96.2 99.4 Retention % Pd 96.3 98.3 98.8 97.0 97.8

1:1 1:2 1:3 1:4 1:6